CN114057999A - Furyl nano composite copolyester material and preparation method and application thereof - Google Patents

Furyl nano composite copolyester material and preparation method and application thereof Download PDF

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CN114057999A
CN114057999A CN202010790347.6A CN202010790347A CN114057999A CN 114057999 A CN114057999 A CN 114057999A CN 202010790347 A CN202010790347 A CN 202010790347A CN 114057999 A CN114057999 A CN 114057999A
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copolyester
furan
furandicarboxylic acid
copolyester material
ethylene glycol
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周光远
李璐
姜敏
王瑞
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08K7/00—Use of ingredients characterised by shape
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C08K2003/3009—Sulfides
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

Abstract

The application discloses a furan-based nano composite copolyester material, which comprises a copolyester matrix and a two-dimensional nano material; the copolyester matrix is mainly formed by copolymerizing 2, 5-furandicarboxylic acid and dihydric alcohol; the dihydric alcohol is at least one of ethylene glycol, 1, 4-butanediol and 1, 6-hexanediol; the two-dimensional nanomaterial is dispersed in a copolyester matrix. And provides a preparation method of the furyl nanometer composite copolyester material. The bio-based content of the furan-based nano composite copolyester material is 100%, the polyester molecular chain structure is regulated and controlled to be hybridized with the two-dimensional nano material by utilizing the synergistic effect of copolymerization and nano composite, the furan-based nano composite copolyester material has the excellent characteristics of good crystallization rate, high elongation at break and good barrier property, and has wide application prospect in the fields of bottle materials, packaging, high-performance fibers, engineering plastics and the like.

Description

Furyl nano composite copolyester material and preparation method and application thereof
Technical Field
The application relates to a furan-based nano composite copolyester material, a preparation method and application thereof, belonging to the technical field of high polymer materials.
Background
2, 5-Furanedicarboxylic acid (FDCA) is one of the furan family members, an important bio-based platform compound, and is abundant in source and can be obtained by dehydrating fructose and galactose. FDCA has a similar structure to petroleum-based terephthalic acid (PTA), one of the raw materials for PET synthesis, is an aromatic compound of a cyclic conjugated system, contains two carboxyl groups, is not renewable, and is considered as an ideal substitute for PTA. Compared with petroleum-based poly (ethylene terephthalate) (PET) and poly (butylene terephthalate) (PBT), the bio-based poly (ethylene 2, 5-furandicarboxylate) (PEF) and poly (butylene 2, 5-furandicarboxylate) (PBF) have more excellent comprehensive performance and wide application prospects in the fields of high-barrier packaging materials, high-performance fibers, engineering plastics and the like. The PEF has better mechanical strength, thermal property and gas barrier property, but has the defects of poor crystallinity and insufficient toughness; PBF has a low glass transition temperature although it has good crystallinity. At present, modification of PEF mainly utilizes diacid or diol monomers introduced with a flexible structure to improve the toughness and crystallization performance of the PEF, but introduction of a flexible unit often causes reduction of the thermal performance and barrier performance of a polyester material; the modification of the PBF mainly improves the glass transition temperature and the barrier property of the material by introducing rigid structural units into the polyester structure, but causes the problems of poor crystallinity and toughness.
Disclosure of Invention
Aiming at the problem of poor comprehensive performance of 2, 5-furyl polyester, the application utilizes a two-dimensional nano material to carry out doping modification on 2, 5-furandicarboxylic acid ethylene glycol-co-butanediol copolyester (PEBF) to prepare the furyl nano composite copolyester material with good crystallization rate, high elongation at break and good barrier property.
A furan-based nano composite copolyester material comprises a copolyester matrix and a two-dimensional nanomaterial;
the copolyester matrix is mainly formed by copolymerizing 2, 5-furandicarboxylic acid and dihydric alcohol;
the dihydric alcohol is at least one of ethylene glycol, 1, 4-butanediol and 1, 6-hexanediol;
the two-dimensional nanomaterial is dispersed in a copolyester matrix.
Optionally, the copolyester matrix is formed by copolymerizing 2, 5-furandicarboxylic acid and dihydric alcohol.
Optionally, the dihydric alcohol is at least one selected from ethylene glycol and 1, 4-butanediol.
Optionally, the diols include ethylene glycol and 1, 4-butanediol.
Optionally, the diols are ethylene glycol and 1, 4-butanediol.
Optionally, the diol is selected from at least one of ethylene glycol and 1, 6-hexanediol.
Optionally, the dihydric alcohol is selected from at least one of ethylene glycol and 1, 4-butanediol, 1, 6-hexanediol.
In the application, the copolyester matrix is 2, 5-furandicarboxylic acid ethylene glycol-co-1, 4-butanediol copolyester (PEBF), 2, 5-furandicarboxylic acid ethylene glycol-co-1, 6-hexanediol copolyester (PEHF), 2, 5-furandicarboxylic acid 1, 4-butanediol-co-1, 6-hexanediol copolyester (PBHF), and the structural formula is shown in the specification
Figure BDA0002623552670000021
2, 5-furandicarboxylic acid, ethylene glycol, 1, 4-butanediol and 1, 6-hexanediol are all biomass source compounds, and the content of the bio-based material of the copolyester matrix is 100%.
Optionally, the number of moles of the two-dimensional nanomaterial is 0.1% to 5% of the number of moles of 2, 5-furandicarboxylic acid.
Optionally, the moles of the two-dimensional nanomaterial are 0.1% to 2% of the moles of 2, 5-furandicarboxylic acid.
Optionally, the moles of the two-dimensional nanomaterial are 0.5% to 1% of the moles of 2, 5-furandicarboxylic acid.
Optionally, the moles of the two-dimensional nanomaterial are any of 0.1%, 1%, 0.1%, 0.5%, 0.7%, 0.9%, 1%, 2%, 5%, or a range between any two, independently selected from the moles of 2, 5-furandicarboxylic acid.
Optionally, the two-dimensional nanomaterial is selected from TiO2ZnO, graphene, boron nitride, silica, MoS2At least one of (1).
Optionally, in the copolyester matrix, the diol structural units comprise ethylene glycol structural units and 1, 4-butanediol structural units.
Optionally, in the copolyester matrix, the diol structural units are an ethylene glycol structural unit and a 1, 4-butanediol structural unit.
Optionally, the molar ratio of ethylene glycol structural units to 1, 4-butanediol structural units in the copolyester matrix is 0.5: 9.5-9.5: 0.5.
alternatively, the molar ratio of ethylene glycol building blocks to 1, 4-butanediol building blocks is 3: 7-6: 4.
optionally, the intrinsic viscosity of the furan-based nanocomposite copolyester material is 0.5-1.6 dL/g.
Optionally, the intrinsic viscosity of the furan-based nanocomposite copolyester material is 0.8-1.3 dL/g.
Optionally, the intrinsic viscosity of the furan-based nanocomposite copolyester material is 0.96-1.31 dL/g.
Optionally, the intrinsic viscosity of the furan-based nanocomposite copolyester material is independently selected from any of 0.5dL/g, 0.8dL/g, 0.9dL/g, 0.96dL/g, 1.0dL/g, 1.08dL/g, 1.1dL/g, 1.11dL/g, 1.15dL/g, 1.18dL/g, 1.20dL/g, 1.21dL/g, 1.24dL/g, 1.26dL/g, 1.28dL/g, 1.29dL/g, 1.30dL/g, 1.31dL/g, or a range between any two.
Optionally, the tensile strength of the furan-based nanocomposite copolyester material is 50-135 MPa.
Optionally, the tensile strength of the furan-based nanocomposite copolyester material is 85-135 MPa.
Optionally, the tensile strength of the furan-based nanocomposite copolyester material is 89-126 MPa.
Optionally, the tensile strength of the furanyl nanocomposite copolyester material is independently selected from any value of 50MPa, 60MPa, 70MPa, 80MPa, 85MPa, 89MPa, 90MPa, 93MPa, 95MPa, 97MPa, 100MPa, 102MPa, 106MPa, 110MPa, 112MPa, 115MPa, 116MPa, 120MPa, 121MPa, 126MPa, 130MPa, 135MPa, or a range between any two.
Optionally, the elongation at break of the furan-based nanocomposite copolyester material is 20% to 1000%.
Optionally, the elongation at break of the furan-based nanocomposite copolyester material is 500% to 1000%.
Optionally, the elongation at break of the furan-based nanocomposite copolyester material is 35% to 859%.
Optionally, the elongation at break of the furanyl nanocomposite copolyester material is independently selected from any value of 20%, 30%, 35%, 50%, 100%, 103%, 105%, 108%, 117%, 125%, 150%, 200%, 250%, 290%, 300%, 310%, 326%, 350%, 400%, 450%, 500%, 600%, 700%, 800%, 850%, 859%, 900%, 950%, 1000%, or a range between any two.
Optionally, the oxygen transmission capacity of the furyl nano composite copolyester material is 0.1-0.0001 cm3/m2·24h·0.1MPa。
Optionally, the oxygen transmission capacity of the furyl nano composite copolyester material is 0.02-0.001 cm3/m2·24h·0.1MPa。
Optionally, the oxygen transmission capacity of the furyl nano composite copolyester material is 0.112-0.001 cm3/m2·24h·0.1MPa。
Optionally, the oxygen transmission capacity of the furan-based nanocomposite copolyester material is independently selected from 0.112cm3/m2·24h·0.1Mpa、0.1cm3/m2·24h·0.1Mpa、0.05cm3/m2·24h·0.1Mpa、0.036cm3/m2·24h·0.1Mpa、0.03cm3/m2·24h·0.1Mpa、0.02cm3/m2·24h·0.1Mpa、0.016cm3/m2·24h·0.1Mpa、0.011cm3/m2·24h·0.1Mpa、0.01cm3/m2·24h·0.1Mpa、0.009cm3/m2·24h·0.1Mpa、0.008cm3/m2·24h·0.1Mpa、0.007cm3/m2·24h·0.1Mpa、0.005cm3/m2·24h·0.1Mpa、0.004cm3/m2·24h·0.1Mpa、0.003cm3/m2·24h·0.1Mpa、0.002cm3/m2·24h·0.1Mpa、0.001cm3/m2Any value or range between any two of 24 h.0.1 MPa.
According to another aspect of the present application, a method for preparing the furan-based nanocomposite copolyester material is provided.
Optionally, the preparation method comprises one of an in-situ compounding method and a melt blending method.
Optionally, the in-situ doping method at least includes:
melting and polymerizing a mixture containing 2, 5-furandicarboxylic acid, dihydric alcohol and a two-dimensional nano material in an inert gas atmosphere under the action of a polyester synthesis catalyst to obtain the furan-based nano composite copolyester material;
the dihydric alcohol is at least one of ethylene glycol, 1, 4-butanediol and 1, 6-hexanediol.
Optionally, the melt blending process comprises at least:
melting and polymerizing a mixture containing 2, 5-furandicarboxylic acid and dihydric alcohol in an inert gas atmosphere under the action of a polyester synthesis catalyst to obtain a copolyester matrix; in the inert gas atmosphere, a mixture containing a copolyester matrix and a two-dimensional nano material is melted and blended to obtain the furan-based nano composite copolyester material;
the dihydric alcohol is at least one of ethylene glycol, 1, 4-butanediol and 1, 6-hexanediol.
Alternatively, the ratio of the molar amount of glycol to the molar amount of 2, 5-furandicarboxylic acid is 1: 1-4: 1.
Alternatively, the ratio of the molar amount of glycol to the molar amount of 2, 5-furandicarboxylic acid is 1.5: 1-2.5: 1.
Alternatively, the ratio of the molar amount of glycol to the molar amount of 2, 5-furandicarboxylic acid is 1.5: 1-2.56: 1.
Alternatively, the ratio of the molar amount of glycol and the molar amount of 2, 5-furandicarboxylic acid is independently selected from 1: 1. 1.25: 1. 1.5: 1. 1.75: 1. 2: 1. 2.25: 1. 2.5: 1. 2.56: 1. 2.75: 1. 3: 1. 3.5: 1. 4:1, or a range of values between any two.
Optionally, the diols include ethylene glycol and 1, 4-butanediol.
Optionally, the diols are ethylene glycol and 1, 4-butanediol.
Optionally, in the dihydric alcohol, the molar ratio of the ethylene glycol to the 1, 4-butanediol is as follows: 0.5: 9.5-9.5: 0.5.
alternatively, the molar ratio of the ethylene glycol to the 1, 4-butanediol is: 3: 7-6: 4.
optionally, the amount of the two-dimensional nano material is 0.1% o to 5% of the mole number of the 2, 5-furandicarboxylic acid.
Optionally, the amount of the two-dimensional nano material is 0.5% o to 5% of the mole number of the 2, 5-furandicarboxylic acid.
Optionally, the amount of the two-dimensional nano material is 0.1-2% of the mole number of the 2, 5-furandicarboxylic acid.
Optionally, the amount of the two-dimensional nano material is 0.5-1% of the mole number of the 2, 5-furandicarboxylic acid.
Optionally, the moles of the two-dimensional nanomaterial are any of 0.1%, 1%, 0.1%, 0.5%, 0.7%, 0.9%, 1%, 2%, 5%, or a range between any two, independently selected from the moles of 2, 5-furandicarboxylic acid.
Optionally, the polyester synthesis catalyst is selected from at least one of titanium-based, antimony-based and zinc-based catalysts.
Optionally, the polyester synthesis catalyst is selected from at least one of tetrabutyl titanate, titanium dioxide, ethylene glycol titanium, stannous oxalate and zinc acetate.
Optionally, the amount of the polyester synthesis catalyst is 0.1-1.5 mol% of the 2, 5-furandicarboxylic acid.
Optionally, the amount of the polyester synthesis catalyst is 0.5-1.0 mol% of 2, 5-furandicarboxylic acid.
Optionally, the amount of the polyester synthesis catalyst is 0.4-0.6 mol% of the 2, 5-furandicarboxylic acid.
Alternatively, the polyester synthesis catalyst is used in an amount such that the proportion of 2, 5-furandicarboxylic acid is independently selected from any of 0.1 mol%, 0.2 mol%, 0.25 mol%, 0.3 mol%, 0.4 mol%, 0.5 mol%, 0.6 mol%, 0.7 mol%, 0.8 mol%, 1.0 mol%, 1.2 mol%, 1.4 mol%, 1.5 mol%, or a range between any two thereof.
Optionally, the melt polymerization comprises at least the following steps;
(1) an esterification stage: reacting at a pressure of 0.1-1 MPa and a temperature of 120-;
(2) a pre-polycondensation stage: reacting at a pressure of 10-200 Pa and a temperature of 200 ℃ and 280 ℃ for 0.5-2 hours;
(3) a polycondensation stage: the reaction is carried out at a pressure of 10-100 Pa and a temperature of 160-260 ℃ for 1-6 hours.
Optionally, the melt blending conditions are: the temperature is 160 ℃ and 260 ℃, and the rotation speed of the screw is 80-300 r/min.
Optionally, the melt blending conditions are: the temperature is 200 ℃ and 230 ℃, and the rotation speed of the screw is 140-180 r/min.
Optionally, the melt blending conditions are: the temperature is 215 ℃, and the screw rotation speed is 160 r/min.
Optionally, the inert gas is selected from at least one of nitrogen and argon.
According to another aspect of the application, the furan-based nanocomposite copolyester material and the application of the furan-based nanocomposite copolyester material prepared by the preparation method of the furan-based nanocomposite copolyester material in bottle materials, packaging, high-performance fibers and engineering plastics are provided.
The beneficial effects that this application can produce include:
according to the furan-based nano composite copolyester material, a two-dimensional nano material is compounded in a copolyester system through an in-situ compounding method or a melt blending method, the toughness of copolyester PEBF is adjusted by adjusting the content of a PBF unit through adjusting the adding ratio of 1, 4-butanediol and ethylene glycol, and the multi-path effect and the permeable area reducing effect can be effectively utilized to reduce the diffusion coefficient and the solubility coefficient of gas in a polymer by compounding the two-dimensional nano material in a polyester matrix, so that the gas permeability coefficient is reduced, and the gas barrier property of the polyester is improved. Therefore, the cooperation of copolymerization and nano-compounding is utilized to regulate and control the hybridization of the polyester molecular chain structure and the two-dimensional nano-material, and the prepared furan-based nano-composite copolyester material has the excellent characteristics of good crystallization rate, high elongation at break and good barrier property, and meanwhile, the furan-based nano-composite copolyester material with the bio-based content of 100% has wide application prospect in the fields of bottle materials, packaging, high-performance fibers, engineering plastics and the like.
Drawings
FIG. 1 shows two-dimensional nano TiO for example2Transmission Electron Microscopy (TEM) test images of (a).
FIG. 2 is a Transmission Electron Microscope (TEM) test chart of calcium carbonate nanoparticles used in the example.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
The raw materials, monomers and catalysts in the examples of the present application were all purchased commercially, unless otherwise specified.
Wherein, the two-dimensional nano TiO2Is prepared from titanium tetrachloride through hydrolyzing, using glycol as solvent, and preparing two-dimensional nano TiO by solvothermal method2。
The analysis method in the examples of the present application is as follows:
transmission Electron Microscopy (TEM) analysis conditions were analyzed using a TECNAI F20 instrument: the acceleration voltage is 200.0 Kv.
The intrinsic viscosity was measured by using phenol/tetrachloroethane (1: lm/m) as a solvent, and a Ubbelohde viscometer at 25. + -. 0.05 ℃.
The determination method of the mechanical property is GBT1040.1-2006, test instrument ASTM D638, test condition: at 25 ℃, wherein
The tensile strength is the maximum tensile stress, MPa, born by the sample in the tensile experiment process;
elongation at break is the increase in unit length of the original gauge length expressed as a dimensionless ratio or percentage (%).
The testing method of the barrier property is GBT19789-2005, and the testing instrument is ASTM D3985-O2And the measurement conditions are as follows: at 25 ℃ and a relative humidity of 50%, wherein O2The transmission is the ratio of the oxygen transmission rate to the difference between the partial pressure of oxygen at both sides of the sample, and the unit is cm3/m224h 0.1MPa, oxygen transmission rate is the amount of oxygen that has permeated through a unit area of the sample per unit time under the experimental conditions, and the unit is mol/m2·s。
In the examples, the normal pressure means 101.3 KPa.
Example 1
Under the protection of nitrogen gas, 0.25mmol of two-dimensional nano TiO2Stirring and mechanically stirring 50mmol of 2, 5-furandicarboxylic acid, 75mmol of ethylene glycol and 0.25mmol of tetrabutyl titanate catalyst until the mixture is uniformly mixed, and heating the system to 220 ℃ under normal pressure to perform esterification reaction for 2.5 hours; the system is subjected to pre-polycondensation reaction by gradient heating to 240 ℃ within 0.5h under the condition of 10 Pa; vacuumizing the reaction system to 10Pa for polycondensation reaction, reacting at 240 ℃ for 4h, and carrying out in-situ compounding to obtain the furyl nano-composite copolyester material. Is recorded as sample # 1.
Example 2
Under the protection of nitrogen gas, 0.25mmol of two-dimensional nano TiO2Stirring and mechanically stirring 50mmol of 2, 5-furandicarboxylic acid, 75mmol of 1, 4-butanediol and 0.25mmol of tetrabutyl titanate catalyst until the components are uniformly mixed, and heating the system to 260 ℃ under normal pressure to perform esterification reaction for 2.5 hours; the system is subjected to pre-polycondensation reaction by gradient heating to 240 ℃ within 0.5h under the condition of 10 Pa; vacuumizing the reaction system to 10Pa for polycondensation reaction, reacting at 240 ℃ for 4h, and carrying out in-situ compounding to obtain the furyl nano-composite copolyester material. Is recorded as sample # 2.
Example 3
Under the protection of nitrogen gas, 0.25mmol of two-dimensional nano TiO250mmol of 2, 5-furandicarboxylic acid and 102.4mmol of ethylene glycolGlycol, 25.6mmol of 1, 4-butanediol and 0.5mmol of tetrabutyl titanate catalyst are stirred mechanically until the mixture is uniformly mixed, and the system is heated to 220 ℃ under normal pressure to carry out esterification reaction for 2.5 hours; the system is subjected to pre-polycondensation reaction by gradient heating to 240 ℃ within 0.5h under the condition of 10 Pa; and carrying out polycondensation reaction at 10Pa, reacting for 4h at 240 ℃, and carrying out in-situ compounding to obtain the furyl nano composite copolyester material. Record as sample # 3.
Example 4
Under the protection of nitrogen gas, 0.25mmol of two-dimensional nano TiO2Stirring and mechanically stirring 50mmol of 2, 5-furandicarboxylic acid, 64mmol of ethylene glycol, 64mmol of 1, 4-butanediol and 0.5mmol of tetrabutyl titanate catalyst until the mixture is uniformly mixed, and carrying out esterification reaction for 2.5h by gradient heating the system to 220 ℃ within 0.5h under normal pressure; the system is heated to 240 ℃ under the condition of 10Pa to carry out pre-polycondensation reaction; vacuumizing the reaction system to 10Pa for polycondensation reaction, reacting at 240 ℃ for 4h, and carrying out in-situ compounding to obtain the furyl nano-composite copolyester material. Is recorded as sample # 4.
Example 5
Under the protection of nitrogen gas, 0.5mmol of two-dimensional nano TiO2Stirring and mechanically stirring 50mmol of 2, 5-furandicarboxylic acid, 102.4mmol of ethylene glycol, 25.6mmol of 1, 4-butanediol and 5mmol of tetrabutyl titanate catalyst until the mixture is uniformly mixed, and heating the system to 220 ℃ under normal pressure to perform esterification reaction for 2.5 hours; the system is subjected to pre-polycondensation reaction by gradient heating to 240 ℃ within 0.5h under the condition of low vacuum 10 Pa; vacuumizing the reaction system to 10Pa for polycondensation reaction, reacting at 240 ℃ for 4h, and carrying out in-situ compounding to obtain the furyl nano-composite copolyester material. Is recorded as sample # 5.
Example 6
Stirring and mechanically stirring 50mmol of 2, 5-furandicarboxylic acid, 102.4mmol of ethylene glycol, 25.6mmol of 1, 4-butanediol and 0.5mmol of tetrabutyl titanate catalyst under the protection of nitrogen gas until the components are uniformly mixed, and heating the system to 220 ℃ under normal pressure to perform esterification reaction for 2.5 hours; the system is subjected to pre-polycondensation reaction by gradient heating to 240 ℃ within 0.5h under the condition of low vacuum 10 Pa; vacuumizing the reaction system to 10Pa for polycondensation reaction, reacting at 240 ℃ for 4h to obtain 2, 5-furandicarboxylic acid ethylene glycol-co-butanediol copolyester, and thenAdding 0.25mmol of two-dimensional nano TiO2Premixing with 50mmol of 2, 5-furandicarboxylic acid ethylene glycol-co-butanediol copolyester, and melting and blending at 215 ℃ under the protection of nitrogen and at the screw rotation speed of 160r/min to obtain the furyl nano composite copolyester material. Record as sample # 6.
Example 7
Stirring and mechanically stirring 50mmol of 2, 5-furandicarboxylic acid, 102.4mmol of ethylene glycol, 25.6mmol of 1, 4-butanediol and 0.5mmol of tetrabutyl titanate catalyst under the protection of nitrogen gas until the components are uniformly mixed, and heating the system to 220 ℃ under normal pressure to perform esterification reaction for 2.5 hours; the system is subjected to pre-polycondensation reaction by gradient heating to 240 ℃ within 0.5h under the condition of low vacuum 10 Pa; vacuumizing the reaction system to 10Pa for polycondensation reaction, reacting for 4h at 240 ℃ to obtain 2, 5-furandicarboxylic acid ethylene glycol-co-butanediol copolyester, and adding 0.5mmol of two-dimensional nano TiO2Premixing with 50mmol of 2, 5-furandicarboxylic acid ethylene glycol-co-butanediol copolyester, and melting and blending at 215 ℃ under the protection of nitrogen and at the screw rotation speed of 160r/min to obtain the furyl nano composite copolyester material. Record as sample # 7.
Example 8
The procedure is as in example 3, except that two-dimensional TiO is used2Replacement of nanosheets by two-dimensional MoS2And nanosheet, the other operations are the same, and the obtained furyl nano composite copolyester material is marked as sample No. 8.
Example 9
The procedure is as in example 6, except that two-dimensional TiO is used2Replacement of nanosheets by two-dimensional MoS2And nanosheet, the other operations are the same, and the obtained furyl nano composite copolyester material is marked as sample No. 9.
Example 10
The operation is the same as that in example 3, except that 1, 4-butanediol is replaced by 1, 6-hexanediol, and the other operations are the same, and the obtained furan-based nanocomposite copolyester material is marked as sample # 10.
Comparative example 1
Stirring and mechanically stirring 50mmol of 2, 5-furandicarboxylic acid, 102.4mmol of ethylene glycol, 25.6mmol of 1, 4-butanediol and 0.5mmol of tetrabutyl titanate catalyst under the protection of nitrogen gas until the components are uniformly mixed, and heating the system to 220 ℃ under normal pressure to perform esterification reaction for 2.5 hours; the system is subjected to pre-polycondensation reaction by gradient heating to 240 ℃ within 0.5h under the condition of low vacuum 10 Pa; vacuumizing the reaction system to 10Pa for polycondensation reaction, and reacting at 240 ℃ for 4h to obtain the 2, 5-furandicarboxylic acid ethylene glycol-co-butanediol copolyester. Record as sample D1 #.
Comparative example 2
Stirring and mechanically stirring 0.25mol of calcium carbonate nano particles, 50mol of 2, 5-furandicarboxylic acid, 102.4mol of ethylene glycol, 25.6mol of 1, 4-butanediol and 0.5mmol of tetrabutyl titanate catalyst under the protection of nitrogen gas until the calcium carbonate nano particles, the 2, 5-furandicarboxylic acid, the ethylene glycol, the 1, 4-butanediol and the tetrabutyl titanate are uniformly mixed, and heating the system to 260 ℃ under normal pressure to perform esterification reaction for 2.5 hours; the system is subjected to pre-polycondensation reaction by gradient heating to 240 ℃ within 0.5h under the condition of low vacuum 10 Pa; vacuumizing the reaction system to 10Pa for polycondensation reaction, reacting at 240 ℃ for 4h, and carrying out in-situ compounding to obtain the furyl nano-composite copolyester material. Record as sample D2 #.
Comparative example 3
The procedure is as in example 6, except that two-dimensional TiO is used2The nanosheets are replaced by calcium carbonate nanoparticles, the other operations are the same, and the obtained furyl nano composite copolyester material is marked as sample D3 #.
The samples prepared in the above examples and comparative examples were subjected to the intrinsic viscosity, mechanical properties and barrier properties test, and the results are shown in table 1.
TABLE 1
Figure BDA0002623552670000111
O2The units of the permeation amount are: cm3/m2·24h·0.1MPa。
As can be seen from Table 1, the performance of the furyl nanocomposite copolyester material is significantly improved by doping the two-dimensional nanomaterial, and compared with sample No. 5, sample No. D1 is prepared by in-situ compounding two-dimensional nano TiO2Tensile strength is increased from 85MPa to 126MPa, elongation at break is increased from 65% to 326%, and O2The permeability is 0.036cm3/m2Decrease of 24 h.0.1 MPa to 0.001cm3/m224 h.0.1 MPa, intrinsic viscosity increased from 0.97dL/g to 1.15 dL/g. The tensile strength and elongation at break of the doped calcium carbonate nano particles D2# are not obviously changed compared with D1 #. The calcium carbonate nano particles are non-two-dimensional nano materials and are prepared by two-dimensional nano TiO2The difference between the TEM image of (FIG. 1) and the TEM image of calcium carbonate nanoparticles (FIG. 2) can be seen, two-dimensional nano-TiO2Is of a lamellar structure and has large diameter-thickness ratio, and the two-dimensional nano material effectively improves the elongation at break and O of the polyester matrix2And (4) barrier rate. Comparing sample D3# with sample 6#, two-dimensional nano TiO is doped by a melt blending method2Elongation at break, O2The penetration and the intrinsic viscosity are both greatly improved. The method utilizes the synergistic effect of copolymerization and nano-compounding to regulate and control the hybridization of the polyester molecular chain structure and the two-dimensional nano-material, and the prepared furan-based nano-composite copolyester material has the excellent characteristics of good crystallization rate, high elongation at break and good barrier property.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.

Claims (10)

1. A furan-based nano composite copolyester material is characterized by comprising a copolyester matrix and a two-dimensional nano material;
the copolyester matrix is mainly formed by copolymerizing 2, 5-furandicarboxylic acid and dihydric alcohol;
the dihydric alcohol is at least one of ethylene glycol, 1, 4-butanediol and 1, 6-hexanediol;
the two-dimensional nanomaterial is dispersed in a copolyester matrix.
2. The furan-based nanocomposite copolyester material according to claim 1, wherein the mole number of the two-dimensional nanomaterial is 0.1 to 5% of the mole number of 2, 5-furandicarboxylic acid;
preferably, the mole number of the two-dimensional nano material is 0.1 to 2 percent of the mole number of the 2, 5-furandicarboxylic acid.
3. The furan-based nanocomposite copolyester material according to claim 1, wherein the two-dimensional nanomaterial is selected from TiO2ZnO, graphene, boron nitride, silica, MoS2At least one of (1).
4. The furan-based nanocomposite copolyester material according to claim 1, wherein the molar ratio of the ethylene glycol structural unit and the 1, 4-butanediol structural unit in the copolyester matrix is 0.5: 9.5-9.5: 0.5;
preferably, the molar ratio of ethylene glycol structural units to 1, 4-butanediol structural units is 3: 7-6: 4.
5. the furan-based nanocomposite copolyester material according to claim 1, wherein the intrinsic viscosity of the furan-based nanocomposite copolyester material is 0.5 to 1.6 dL/g;
preferably, the intrinsic viscosity of the furan-based nanocomposite copolyester material is 0.8-1.3 dL/g;
preferably, the tensile strength of the furyl nano composite copolyester material is 50-135 MPa;
preferably, the tensile strength of the furyl nano composite copolyester material is 85-135 MPa;
preferably, the elongation at break of the furan-based nanocomposite copolyester material is 20-1000%;
preferably, the breaking elongation of the furan-based nanocomposite copolyester material is 500-1000%;
preferably, the oxygen transmission capacity of the furyl nano composite copolyester material is 0.1-0.0001 cm3/m2·24h·0.1MPa；
Preferably, the oxygen transmission capacity of the furan-based nanocomposite copolyester material is 0.02～0.001cm3/m2·24h·0.1MPa。
6. The method for preparing furan-based nanocomposite copolyester material according to any one of claims 1 to 5, wherein the preparation method comprises one of an in-situ compounding method and a melt blending method.
7. The method for preparing furan-based nanocomposite copolyester material according to claim 6, wherein the in-situ compounding method at least comprises:
melting and polymerizing a mixture containing 2, 5-furandicarboxylic acid, dihydric alcohol and a two-dimensional nano material in an inert gas atmosphere under the action of a polyester synthesis catalyst to obtain the furan-based nano composite copolyester material;
the dihydric alcohol is at least one of ethylene glycol, 1, 4-butanediol and 1, 6-hexanediol.
8. The method for preparing furan-based nanocomposite copolyester material according to claim 6, wherein the melt blending method at least comprises:
melting and polymerizing a mixture containing 2, 5-furandicarboxylic acid and dihydric alcohol in an inert gas atmosphere under the action of a polyester synthesis catalyst to obtain a copolyester matrix; in the inert gas atmosphere, a mixture containing a copolyester matrix and a two-dimensional nano material is melted and blended to obtain the furan-based nano composite copolyester material;
the dihydric alcohol is at least one of ethylene glycol, 1, 4-butanediol and 1, 6-hexanediol.
9. The process for preparing furan-based nanocomposite copolyester material according to claim 7 or 8, wherein the ratio of the molar amount of the diol to the molar amount of the 2, 5-furandicarboxylic acid is 1: 1-4: 1;
preferably, the ratio of the molar amount of glycol to the molar amount of 2, 5-furandicarboxylic acid is 1.5: 1-2.5: 1;
preferably, in the dihydric alcohol, the molar ratio of the ethylene glycol to the 1, 4-butanediol is as follows: 0.5: 9.5-9.5: 0.5;
preferably, the molar ratio of the ethylene glycol to the 1, 4-butanediol is as follows: 3: 7-6: 4;
preferably, the amount of the two-dimensional nano material is 0.1 per thousand to 5 percent of the mole number of the 2, 5-furandicarboxylic acid;
preferably, the amount of the two-dimensional nano material is 0.1 per thousand to 2 percent of the mole number of the 2, 5-furandicarboxylic acid;
preferably, the polyester synthesis catalyst is selected from at least one of titanium-series, antimony-series and zinc-series catalysts;
preferably, the polyester synthesis catalyst is selected from at least one of tetrabutyl titanate, titanium dioxide, ethylene glycol titanium, stannous oxalate and zinc acetate;
preferably, the amount of the polyester synthesis catalyst is 0.1-1.5 mol% of 2, 5-furandicarboxylic acid;
preferably, the amount of the polyester synthesis catalyst is 0.5-1.0 mol% of 2, 5-furandicarboxylic acid;
preferably, the melt polymerization comprises at least the following steps;
(1) an esterification stage: reacting at a pressure of 0.1-1 MPa and a temperature of 120-;
(2) a pre-polycondensation stage: reacting at a pressure of 10-200 Pa and a temperature of 200 ℃ and 280 ℃ for 0.5-2 hours;
(3) a polycondensation stage: reacting at a pressure of 10-100 Pa and a temperature of 160-260 ℃ for 1-6 hours;
preferably, the melt blending conditions are: the temperature is 160 ℃ and 260 ℃, and the rotation speed of the screw is 80-300 r/min.
10. Use of the 2, 5-furandicarboxylic acid copolyester of claims 1 to 5, the furan-based nanocomposite copolyester material prepared by the method for preparing the furan-based nanocomposite copolyester material of any one of claims 6 to 9 in bottle materials, packaging, high-performance fibers and engineering plastics.
CN202010790347.6A 2020-08-07 2020-08-07 Furyl nano composite copolyester material and preparation method and application thereof Pending CN114057999A (en)

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