CN108997568A - A kind of biological poly ester material and its preparation method and application - Google Patents

Abstract

The invention discloses a kind of biological poly ester materials, including 2,5-furandicarboxylic acid binary alcohol esters soft segment unit shown in 2,5-furandicarboxylic acid binary alcohol esters hard section unit and formula (II) shown in formula (I).Preparation method is also disclosed, by regulating and controlling the biology base thermoplastic polyester material that soft or hard segment unit ratio can get High-tenacity high-strength and appearance color improves, meets the needs of Different Package market.Preparation method simple possible of the present invention, is conducive to industrial applications.

Description

A kind of bio-based polyester material and its preparation method and application

technical field

The invention relates to the field of preparation of polymer materials, in particular to a bio-based polyester material and its preparation method and application.

Background technique

Polyethylene terephthalate (PET) is a thermoplastic polyester widely used in the packaging industry. It is prepared from the polymerization reaction of petroleum-based monomer terephthalic acid (TPA) and ethylene glycol. However, while its massive production and application bring great convenience to human life, it will inevitably lead to a series of problems such as resource shortage and environmental damage.

2,5-furandicarboxylic acid (FDCA) is a bio-based monomer derived from renewable biomass resources such as cellulose and hemicellulose. Monomer TPA has similar structure and properties. Therefore, bio-based polymers derived from FDCA have received extensive attention, especially polyethylene 2,5-furandicarboxylate (PEF). Compared with PET, PEF not only has a higher glass transition temperature and higher tensile modulus and strength, but also has higher gas barrier properties, and its gas permeability coefficients for oxygen and carbon dioxide are 1/3 of those of PET. 11 times and 1/19 times. Therefore, PEF has broad application prospects in the field of packaging materials that require high gas barrier properties.

However, due to the low thermal stability of FDCA and the limitations of the PEF synthesis process, the synthetic PEF polyester has a darker color (yellow-brown or dark brown), and the elongation at break of PEF is only about 3%, which is typical brittle materials. These factors seriously restrict the application of PEF in the plastic packaging industry. In addition, polytrimethylene 2,5-furandicarboxylate (PPF) also has the problem of brittleness. Therefore, PEF and PPF must be toughened and modified to have certain practical value. At present, the toughening modification of PEF mainly focuses on the introduction of dibasic acid or diol monomers containing soft segments or symmetrical rigid structures for copolymerization modification. Copolymerization with dibasic acids significantly reduces the content of furan rings, resulting in a significant drop in gas barrier properties, so copolymerization with dibasic acids is not a good choice. In addition, the introduction of dibasic acids containing soft segments can significantly reduce the tensile modulus and strength of PEF while toughening PEF. For example, for poly(2,5-furandicarboxylic acid/ethylene sebacate) (PESeF) (RSC Advances, 2017, 7 : 13789-13807), when the addition of sebacic acid reaches 70mol%, its elongation at break reaches 1500%, which is significantly improved compared with PEF, but the tensile strength is only 26MPa, which is 64% lower than PEF. The introduction of a diol monomer containing a symmetrical cyclic rigid structure is beneficial to maintain the gas barrier, tensile modulus and strength of PEF while improving the elongation at break (ductility) of PEF, but there must be It is necessary to introduce a large amount of such comonomers to obtain obvious toughening effect, but such comonomers are expensive, and their production technology is monopolized by foreign countries. In addition, its improvement of the impact strength (impact toughness) of PEF is very limited. For example, for poly(ethylene glycol 2,5-furandicarboxylate-co-1,4-cyclohexanedimethanol) (PECF) (Green Chemistry, 2016, 18:5142-5150), when 75mol% 1,4-cyclohexanedimethanol monomer, the elongation at break of the formed copolyester can be increased to 79%, and the tensile modulus and strength are 37% and 18% lower than those of PEF, but the impact strength (4.0k g.cm/cm) is only 1.3 times higher than PEF.

To sum up, for the application of PEF and PPF bio-based polyesters in plastic packaging, it is necessary to overcome the shortcomings of polyesters such as darker color and greater brittleness. In terms of toughening PEF and PPF, there are still some deficiencies, mainly manifested in the obvious decrease in tensile modulus, strength and gas barrier properties while toughening; comonomers with good toughening effects have high cost and large dosage ; The effect of improving the impact toughness is not obvious. Therefore, it is an urgent problem to select suitable comonomers to prepare 2,5-furandicarboxylic acid copolyesters with balanced mechanical properties.

Contents of the invention

Aiming at the defects of darker color and greater brittleness in the prior art when PEF and PPF bio-based polyesters are used as plastic packaging materials, the present invention provides a bio-based polyester material and its preparation method and application. Ester materials offer light color and high toughness while maintaining high tensile strength.

The first aspect of the present invention provides a bio-based polyester material, including 2,5-furandicarboxylate hard segment units represented by formula (I) and 2,5-furan represented by formula (II) dicarboxylic acid glycol ester soft segment unit,

R ₁ is selected from one or more of them;

_{R2 is} selected from one or more of them;

_{R3 is} selected from One or more of -CH ₂ CH ₂ CH ₂ CH ₂ -;

x is an integer of 2-4, y is an integer of 4-70, and z is an integer of 5-55;

-R ₂ -is the residue of HO-R ₂ -OH, the molecular weight of HO-R ₂ -OH is 300-3000g/mol;

Wherein, the -R ₂ - segment accounts for 1-35 wt% of the bio-based polyester material.

In the present invention, the modulus and tensile strength of the PEF are not obviously reduced while improving the ductility and toughness of the PEF by adding the soft segment unit of 2,5-furandicarboxylate.

R ₂ can be set according to actual needs, preferably, R ₂ is Wherein, the definitions of y and z are as mentioned above. Choosing R ₂ with a longer carbon chain has better flexibility, better toughening effect on rigid PEF, and better hydrophobicity. If R ₂ with a symmetrical dimethyl substitution structure is selected, the force between molecular chains is greater and the gas barrier property is stronger.

The bio-based polyester material in the present invention has a light color. According to the Lab color model, the L value of the bio-based polyester material is above 60, the a value is below 5, and the b value is below 10.

Preferably, the molecular weight of the HO-R ₂ -OH is 500-2000 g/mol, and the L value of the bio-based polyester material of the present invention increases as the molecular weight of the HO-R ₂ -OH used increases. However, when the HO-R ₂ -OH molecular weight exceeds 2000g/mol, the length of the soft segment structural unit of the synthesized 2,5-furandicarboxylic acid glycol ester is too large, and the crystallinity is too strong, causing it to react with 2,5-furandicarboxylate The compatibility of the hard segment unit of diol formate is too poor, and the degree of phase separation is too high. This kind of structural defect is not conducive to the mechanical properties of the bio-based polyester material; when the molecular weight of HO-R ₂ -OH is low At 500g/mol, the length of the soft segment structural unit of the synthesized diol 2,5-furandicarboxylate is too low, and the flexibility provided within the unit length is insufficient, which is also not conducive to the mechanical properties of the bio-based polyester material. Further preferably, the molecular weight of the HO-R ₂ -OH is 1000-2000 g/mol.

Preferably, the -R ₂ - segment accounts for 1-20 wt% of the bio-based polyester material, the bio-based polyester material has light color and high tensile toughness, the L value is above 60, and the a value is 5 or less, the b value is less than 10, the elongation at break is not less than 30%, while maintaining high tensile strength, the tensile strength is not less than 50MPa.

Preferably, the -R ₂ - segment accounts for 20-35 wt% of the bio-based polyester material, the bio-based polyester material has light color and high tensile and impact toughness, the L value is above 60, a The value is less than 5, the b value is less than 8, the elongation at break is not less than 200%, the impact strength is not less than 4KJ/m ² , while maintaining high tensile strength, the tensile strength is not less than 40MPa.

Further preferably, the -R ₂ - segment accounts for 33-35 wt% of the bio-based polyester material, the bio-based polyester material has light color and high tensile and impact toughness, the L value is above 60, a The value is less than 5, the b value is less than 8, the elongation at break is not less than 250%, the impact strength is not less than 20KJ/m ² , while maintaining high tensile strength, the tensile strength is not less than 40MPa.

The second aspect of the present invention provides the preparation method of described bio-based polyester material, it comprises the following steps:

(1) Under the action of catalyst A, monomer a, monomer b and monomer c undergo esterification/transesterification reaction to obtain an intermediate;

(2) The intermediate obtained in step (1) is mixed with catalyst B, heated up and subjected to a reduced-pressure compression polymerization reaction, to obtain the bio-based polyester material;

The monomer a is 2,5-furandicarboxylic acid, 2,5-furandicarboxylic acid diester or a mixture thereof; wherein, 2,5-furandicarboxylic acid diester is 2,5-furandicarboxylic acid dimethyl ester or diethyl 2,5-furandicarboxylate;

The monomer b is ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,4-cyclohexanedimethanol, 1,4-cyclohexanediol and 2,2,4,4 - one or more of tetramethyl-1,3-cyclobutanediol;

The monomer c is one or more of polyethylene glycol, polypropylene glycol, polytetramethylene glycol and polyisobutylene glycol.

The catalyst A is n-butyl titanate, isopropyl titanate, stannous octoate, stannous oxalate, dibutyl tin oxide, lithium acetate, potassium acetate, calcium acetate, magnesium acetate, barium acetate, zinc acetate, acetic acid One or more of cobalt, antimony acetate, lead acetate, manganese acetate, silica/titania compound, silica/titanium dioxide/nitrogen-containing compound and silica/titanium dioxide/phosphorous compound kind.

The amount of the catalyst A used is 0.005-0.5 mol% of the molar amount of the monomer a added.

The catalyst B is n-butyl titanate, isopropyl titanate, titanium ethylene glycol, titanium acetylacetonate, antimony ethylene glycol, antimony trioxide, antimony acetate, zinc acetate, manganese acetate, lead acetate, calcium acetate, Cobalt acetate, potassium acetate, magnesium acetate, barium acetate, lithium acetate, silica/titania complex, silica/titania/nitrogen-containing compound and silica/titania/phosphorous compound one or more of.

The amount of catalyst B used is 0.005-0.5 mol% of the molar amount of monomer a added in step (1).

Preferably, an auxiliary agent is added in step (1) or (2), and the auxiliary agent is one or more of a heat stabilizer, a light stabilizer and an inorganic filler, and the amount of the auxiliary agent is a Add 0.1-20wt% of the mass.

Further, the heat stabilizer is 1010, 1076, 425, 330, 1178, 618, 626, 168, TDD, trimethyl phosphite, triethyl phosphite, triisooctyl phosphite, triisodecyl phosphite ester, trilauryl phosphite, tri(tridecyl) phosphite, trioctadecyl phosphite, triphenyl phosphite, tri-p-cresyl phosphite, diphenyltridecyl phosphite ester, tris(2,4-di-tert-butylphenyl) phosphite, pentaerythritol bis(2,4-tert-butylphenyl) diphosphite, bis(2,4-di-p-isopropylphenyl) Pentaerythritol Diphosphite Phosphoric Acid, Pentaerythritol Tetraphosphite Phenyltridecyl, Pentaerythritol Diphosphite Tridecyl, Pentaerythritol Diphosphite Diisodecyl, Pentaerythritol Dioctadecyl Phosphite, Phosphoric Acid, Phosphorous Acid , one or more of polyphosphoric acid and triethyl phosphonoacetate.

The light stabilizer is 791, 700, 783, 119, 770, 622, 944, 2,2,6,6-tetramethyl-4-piperidine stearate, bis(2,2,6,6 -Tetramethyl-4-piperidinyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, 2-hydroxy-4-n- Octyloxybenzophenone, (3,5-di-tert-butyl-2-hydroxyphenyl)-5-chlorobenzotriazole and poly(1-hydroxyethyl-2,2,6,6-tetra One or more of methyl-4-hydroxypiperidine) succinate.

The inorganic filler is one or more of nano-silica, nano-titanium dioxide, nano-calcium carbonate, nano-talcum powder and nano-phyllosilicate.

In step (1), the molar ratio of monomer b to monomer a is 1.1-3:1; the amount of monomer c accounts for 0.5-50 wt% of the total mass fraction of monomer a and monomer c.

In a preferred embodiment of the present invention, the amount of monomer c accounts for 0.5-25 wt% of the total mass fraction of monomer a and monomer c.

In another preferred solution of the present invention, the amount of monomer c accounts for 25-50 wt% of the total mass fraction of monomer a and monomer c.

In step (1), the temperature of the esterification/transesterification reaction is 170-210° C., and the reaction time is 1-10 h.

In step (2), the temperature of the pressure reduction polymerization reaction is 210-260° C., the system pressure is ≤200 Pa, and the polycondensation time is 1-8 hours.

The third aspect of the present invention provides the application of the bio-based polyester material, including one or more of packaging materials, medical materials, fibers and engineering plastics.

Compared with the prior art, the present invention has the following beneficial effects:

(1) The light-colored high-toughness and high-strength bio-based polyester material prepared by the present invention is made of 2,5-furandicarboxylic acid or 2.5-furandicarboxylic acid diester, ethylene glycol or 1,3-propanediol or butanediol and commonly used The polyether diol and/or polyisobutylene diol are prepared as raw materials, the preparation method is simple and easy, and the cost is low, which is beneficial to industrial application.

(2) The light-colored high-toughness high-bio-based polyester material prepared by the present invention can have good color and mechanical properties when introducing 1-20 wt% of commonly used polyether diols and/or polyisobutylene diol segments. The advantages of balanced performance, the tensile strength is not less than 50MPa, and the elongation at break is not less than 30%.

(3) The light-colored high-toughness and high-strength bio-based polyester material prepared by the present invention can undergo obvious brittle-ductile transition when 20-35wt% of commonly used polyether diols and/or polyisobutylene diol segments are introduced , and its tensile strength is not less than 40MPa, its elongation at break is not less than 200%, and its impact strength is not less than 4KJ/m ² .

(4) The light-colored bio-based polyester material with controllable mechanical properties prepared by the present invention can adjust the content of each component through the feeding ratio to meet different packaging market needs.

Description of drawings

Fig. 1 is the appearance figure of the sample prepared by comparative examples 1-4 and embodiments 1-4;

Fig. 2 is the nuclear magnetic spectrum of the sample prepared by comparative examples 1～4 and embodiment 2 and 4;

Fig. 3 is a tensile curve diagram of samples prepared in Comparative Examples 1-4 and Examples 2 and 4.

Detailed ways

The test analysis method adopted in following embodiment and comparative example is as follows:

Color L, a, b value determination: According to the Lab color model, L represents the brightness of the sample color, a represents the red-green value of the sample color, and b represents the blue-yellow value of the sample color. Measured by the TES-135 spectroscopic analyzer produced by Taiwan Taishi Electronics.

Intrinsic viscosity: the intrinsic viscosity of the samples in the examples was measured by Hangzhou Zhongwang automatic viscometer, the test temperature was 25°C, and the solvent used was phenol/tetrachloroethane (mass ratio w/w=3/2).

Structural characterization: Bruker AC-80 400M nuclear magnetic resonance instrument was used to test the polymer structure, with deuterated trifluoroacetic acid as solvent and tetramethylsilane as internal standard.

Mechanical properties: A dumbbell-shaped sample with a thickness of 2 mm and a width of 4 mm was prepared using a HaakeMiniJet II micro-injection molding machine. According to the ASTM D638 standard, the tensile test was carried out at 25°C and a tensile rate of 10 mm/min using a Roell Z020 universal material testing machine from Zwick Company, Germany. Five splines were tested for each sample, and the average value was taken as the test result. For brittle fracture samples, such as PEF, the tensile strength is expressed by the breaking strength, and for other ductile fracture samples with yield phenomenon, the tensile strength is expressed by the tensile yield strength.

Impact performance: HaakeMiniJet II micro-injection molding machine is used to prepare a rectangular parallelepiped specimen with a length of 80mm, a width of 4mm, and a thickness of 2mm, and a 2mm deep V-shaped notch is punched on a CEAST notch machine in advance, and a notched Izod impact test is performed on a CEAST pendulum impact instrument , The impact hammer energy is 5.5J. Five splines were tested for each sample, and the average value was taken as the test result.

The present invention will be further specifically described below in conjunction with specific embodiments. The following examples are only for illustrating the present invention, but the present invention is not limited to these examples.

Comparative example 1

(1) Add 66.28g dimethyl 2,5-furandicarboxylate, 44.67g ethylene glycol and 0.1g tetrabutyl titanate to a reactor under nitrogen atmosphere, react at 170°C for 1 hour, and react at 180°C for 1 hour, React at 190°C for 1 hour, and react at 200°C for 1 hour to obtain the transesterified product;

(2) Add 0.1g of ethylene glycol antimony to the esterification product obtained in step (1), and polycondense for 3 hours at 240°C and high vacuum (≦133Pa) to obtain polyethylene 2,5-furandicarboxylate Glycol ester, denoted as PEF, its properties are shown in Table 1.

Comparative example 2

(1) Add 60g 2,5-dimethyl furandicarboxylate, 40.43g ethylene glycol in the reactor of nitrogen atmosphere, 39.56g molecular weight is 1000g/mol polytetramethylene glycol and 0.1g tetrabutyl titanate, in React at 170°C for 1 hour, 180°C for 1 hour, 190°C for 1 hour, and 200°C for 1 hour to obtain the esterified product;

(2) Add 0.1 g of tetrabutyl titanate to the esterification product obtained in step (1), and polycondense for 3 hours at 240°C and high vacuum (≦133Pa) to obtain poly-2,5-furandicarboxylic acid Ethylene glycol-mb-polytetramethylene glycol ester block copolymer. The polytetramethylene glycol segment accounts for 40% of the mass fraction of the copolymer, which is recorded as PET ^1K F-40, and its properties are shown in Table 1.

Comparative example 3

(1) Add 50g 2,5-dimethyl furandicarboxylate, 33.69g ethylene glycol in the reactor of nitrogen atmosphere, 49.46g molecular weight is 1000g/mol polytetramethylene glycol and 0.1g tetrabutyl titanate, in React at 170°C for 1 hour, 180°C for 1 hour, 190°C for 1 hour, and 200°C for 1 hour to obtain the esterified product;

(2) Add 0.1 g of tetrabutyl titanate to the esterification product obtained in step (1), and polycondense for 3 hours at 240°C and high vacuum (≦133Pa) to obtain poly-2,5-furandicarboxylic acid Ethylene glycol-mb-polytetramethylene glycol ester block copolymer. The polytetramethylene glycol segment accounts for 50% of the mass fraction of the copolymer, which is recorded as PET ^1K F-50, and its properties are shown in Table 1.

Comparative example 4

(1) Add 42g 2,5-dimethyl furandicarboxylate, 28.31g ethylene glycol in the reactor of nitrogen atmosphere, 62.31g molecular weight is 1000g/mol polytetramethylene glycol and 0.1g tetrabutyl titanate, in React at 170°C for 1 hour, 180°C for 1 hour, 190°C for 1 hour, and 200°C for 1 hour to obtain the esterified product;

(2) Add 0.1 g of tetrabutyl titanate to the esterification product obtained in step (1), and polycondense for 3 hours at 240°C and high vacuum (≦133Pa) to obtain poly-2,5-furandicarboxylic acid Ethylene glycol-mb-polytetramethylene glycol ester block copolymer. The polytetramethylene glycol segment accounts for 60% of the mass fraction of the copolymer, which is recorded as PET ^1K F-60, and its properties are shown in Table 1.

Example 1

(1) Add 66.28g 2,5-dimethyl furandicarboxylate, 44.67g ethylene glycol in the reactor of nitrogen atmosphere, 7.28g molecular weight is 1000g/mol polytetramethylene glycol and 0.1g tetrabutyl titanate, React at 170°C for 1 hour, 180°C for 1 hour, 190°C for 1 hour, and 200°C for 1 hour to obtain an esterified product;

(2) Add 0.1 g of tetrabutyl titanate to the esterification product obtained in step (1), and polycondense for 3 hours at 240°C and high vacuum (≦133Pa) to obtain poly-2,5-furandicarboxylic acid Ethylene glycol-mb-polytetramethylene glycol ester block copolymer. The polytetramethylene glycol segment accounts for 10% of the mass fraction of the copolymer, which is recorded as PET ^1K F-10, and its properties are shown in Table 1.

Example 2

(1) Add 66.28g 2,5-dimethyl furandicarboxylate, 44.67g ethylene glycol in the reactor of nitrogen atmosphere, 16.4g molecular weight is 1000g/mol polytetramethylene glycol and 0.1g tetrabutyl titanate, React at 170°C for 1 hour, 180°C for 1 hour, 190°C for 1 hour, and 200°C for 1 hour to obtain an esterified product;

(2) Add 0.1 g of tetrabutyl titanate to the esterification product obtained in step (1), and polycondense for 3 hours at 240°C and high vacuum (≦133Pa) to obtain poly-2,5-furandicarboxylic acid Ethylene glycol-mb-polytetramethylene glycol ester block copolymer. The polytetramethylene glycol segment accounts for 20% of the mass fraction of the copolymer, which is recorded as PET ^1K F-20, and its properties are shown in Table 1.

Example 3

(1) Add 66.28g 2,5-dimethyl furandicarboxylate, 44.67g ethylene glycol in the reactor of nitrogen atmosphere, 21.85g molecular weight is 1000g/mol polytetramethylene glycol and 0.1g tetrabutyl titanate, React at 170°C for 1 hour, 180°C for 1 hour, 190°C for 1 hour, and 200°C for 1 hour to obtain an esterified product;

(2) Add 0.1 g of tetrabutyl titanate to the esterification product obtained in step (1), and polycondense for 3 hours at 240°C and high vacuum (≦133Pa) to obtain poly-2,5-furandicarboxylic acid Ethylene glycol-mb-polytetramethylene glycol ester block copolymer. The polytetramethylene glycol segment accounts for 25% of the mass fraction of the copolymer, which is recorded as PET ^1K F-25, and its properties are shown in Table 1.

Example 4

(1) In the reactor of nitrogen atmosphere, add 66.28g 2,5-dimethyl furandicarboxylate, 44.67g ethylene glycol, 28.1g molecular weight is the polytetramethylene glycol of 1000g/mol and 0.1g tetrabutyl titanate, React at 170°C for 1 hour, 180°C for 1 hour, 190°C for 1 hour, and 200°C for 1 hour to obtain an esterified product;

(2) Add 0.1 g of tetrabutyl titanate to the esterification product obtained in step (1), and polycondense for 3 hours at 240°C and high vacuum (≦133Pa) to obtain poly-2,5-furandicarboxylic acid Ethylene glycol-mb-polytetramethylene glycol ester block copolymer. The polytetramethylene glycol segment accounts for 30% of the mass fraction of the copolymer, which is recorded as PET ^1K F-30, and its properties are shown in Table 1.

Example 5

(1) Add 66.28g 2,5-dimethyl furandicarboxylate, 44.67g ethylene glycol in the reactor of nitrogen atmosphere, 32.29g molecular weight is 1000g/mol polytetramethylene glycol and 0.1g tetrabutyl titanate, React at 170°C for 1 hour, 180°C for 1 hour, 190°C for 1 hour, and 200°C for 1 hour to obtain an esterified product;

(2) Add 0.1 g of tetrabutyl titanate to the esterification product obtained in step (1), and polycondense for 3 hours at 240°C and high vacuum (≦133Pa) to obtain poly-2,5-furandicarboxylic acid Ethylene glycol-mb-polytetramethylene glycol ester block copolymer. The polytetramethylene glycol segment accounts for 33% of the mass fraction of the copolymer, which is recorded as PET ^1K F-33, and its properties are shown in Table 1.

Table 1 Prepared sample performance parameter table

The samples prepared above were tested for color L, a, b value, and the results are shown in Table 1. The test results show that the L value of the synthesized block copolyester is significantly higher than that of PEF, and its a and b values are significantly lower than that of PEF, indicating that polytetramethylene glycol segment (PTM G) can effectively improve the color of PEF polyester, This point can also be seen intuitively from the sample diagram shown in Figure 1. Therefore, the above results show that PTMG can significantly improve the color of PEF, and the synthesized PET ^1K F block copolyester is light white gray.

The intrinsic viscosity test was carried out on the samples prepared above, and the results are shown in Table 1. The test results show that the intrinsic viscosity of the synthesized samples exceeds 0.8dL/g, indicating that high molecular weight PEF and PET ^1K F block copolyesters were successfully synthesized.

NMR tests were carried out on the samples prepared above, and the results are shown in Figure 2. The test results show that the peak at δ=7.46 corresponds to the chemical shift of the H atom (F) on the furan ring; the peak at δ=4.88 corresponds to the hard segment chain of ethylene glycol furandicarboxylate The chemical shift of the H atom (a) on the methylene group connected to the ester group in the segment (EF segment); the peaks at δ=4.76 (h) and δ=4.25 (i) correspond to the diethylene glycol chain Section; The spectral peaks at δ=3.81 and δ=1.82 respectively correspond to the chemical shifts and The H atom (d+g) on the methylene group adjacent to the ether bond; affected by the ester groups at both ends, the H atoms on the two methylene groups at both ends of PTMG move to the downfield respectively, respectively δ=4.03(b ) and δ=2.08(c). The above results show that the PET ^1K F block copolyester was successfully synthesized. In addition, the content of PTMG in the synthesized block copolyester can be calculated from the area of the corresponding proton peak on the spectrum, and the calculation result is consistent with the theoretical result.

The samples prepared above were tested for tensile properties and notched impact strength. The results are shown in Table 1, and the tensile curves of Examples 2 and 4 and Comparative Examples 1-4 are shown in FIG. 3 . There is no yield phenomenon in the stretching process of PEF polyester, showing typical hard and brittle characteristics, its tensile strength is 84MPa, and the elongation at break is only 3%. However, for PET ^1K F block copolyester, the mechanical properties of PET ^1K F copolyester gradually changed with the increase of PTMG content. When the PTM G component content is 10-20wt%, the elongation at break of PET ^1K F block copolyester is 104-252%, which is 35 times and 84 times higher than that of pure PEF. The strength is 79-74MPa, and the tensile strength is only 6-12% lower than that of pure PEF, indicating that a lower content of PTM G can significantly improve the ductility of PEF without significantly reducing its tensile strength.

When the content of PTM G is further increased to 20-35wt%, the elongation at break of PET ^1K F block copolyester increases slightly, and the tensile strength drops to 40MPa, but at the same time, it is found that its impact strength has a significant sudden change. It shows that when 20-35wt% of PTMG chain segments are introduced, the PEF can undergo a more obvious brittle-ductile transition, and at this time it still has a certain tensile strength (40MPa).

However, when the content of PTM G component is further increased to more than 40wt%, the elongation at break of PET ^1K F block copolyester can be increased to 684%, and the impact is continuous, but its tensile strength is reduced to less than 30MPa, The obvious mechanical properties of polyester elastomers are no longer suitable for plastic packaging requirements that require high tensile strength.

Example 6

(1) Add 65g of 2,5-furandicarboxylic acid, 51.67g of ethylene glycol, 32.5g of polytetramethylene glycol with a molecular weight of 2000g/mol and 0.12g of isopropyl titanate and 0.25g of heat stabilized Reagent 1010, react at 170°C for 1 hour, 180°C for 1 hour, 190°C for 1 hour, and 200°C for 1 hour to obtain an esterified product;

(2) Add 0.11g of tetrabutyl titanate to the esterification product obtained in step (1), and polycondense for 3 hours at 240°C and high vacuum (≦133Pa) to obtain poly-2,5-furandicarboxylic acid Ethylene glycol-mb-polytetramethylene glycol ester block copolymer. The polytetramethylene glycol segment accounts for 30% of the mass fraction of the copolymer, which is recorded as PET ^2K F-30.

After testing, the L, a, and b values of PET ^2K F-30 are 72, 4, and 3 respectively, the tensile strength is 52MPa, the elongation at break is 104%, and the impact strength is 4.1KJ/m ² .

Example 7

(1) In the reactor of nitrogen atmosphere, add 42g 2,5-furandicarboxylic acid, 33.39g ethylene glycol, 12.3g molecular weight is the polytetramethylene glycol of 2000g/mol and 0.12g stannous oxalate and 0.18g bis(2, 2,6,6-Tetramethyl-4-piperidinyl) sebacate was reacted at 170°C for 1 hour, 180°C for 1 hour, 190°C for 1 hour, and 200°C for 1 hour to obtain an esterified product;

(2) Add 0.08g of antimony dioxide to the esterification product obtained in step (1), and polycondense for 4 hours at 230°C and high vacuum (≦133Pa) to obtain polyethylene 2,5-furandicarboxylate Alcohol-mb-polytetramethylene glycol ester block copolymer. The polytetramethylene glycol segment accounts for 20% of the mass fraction of the copolymer, which is recorded as PET ^2K F-20.

After testing, the L, a, and b values of PET ^2K F-20 are 71, 4, and 9 respectively, the tensile strength is 76MPa, the elongation at break is 71%, and the impact strength is 2.1KJ/m ² .

Example 8

(1) Add 65.67g 2,5-dimethyl furandicarboxylate, 47.51g ethylene glycol in the reactor of nitrogen atmosphere, 16.4g molecular weight is the polyethylene glycol of 1000g/mol and 0.1g stannous oxalate, at 170 ℃ for 1 hour, 180 ℃ for 1 hour, 190 ℃ for 1 hour, 200 ℃ for 1 hour to obtain the transesterification product;

(2) Add 0.13 g of ethylene glycol antimony to the transesterification product obtained in step (1), and polycondense for 3 hours at 240 ° C and high vacuum (≦133 Pa) to obtain polyethylene 2,5-furandicarboxylate Diol-mb-polyethylene glycol ester block copolymer. The polyethylene glycol chain segment accounts for 20% of the mass fraction of the copolymer, which is recorded as PEE ^1K F-20.

After testing, the L, a, and b values of PEE ^1K F-20 are 62, 4, and 9 respectively, the tensile strength is 66MPa, the elongation at break is 112%, and the impact strength is 2.1KJ/m ² .

Example 9

(1) In the reactor of nitrogen atmosphere, add 68.28g 2,5-dimethyl furandicarboxylate, 53.97g propylene glycol, 28.1g molecular weight is the polytetramethylene glycol of 2000g/mol and 0.06g silicon dioxide/titanium dioxide composite and 1.78g of nano-silica, reacted at 170°C for 1 hour, 180°C for 1 hour, 190°C for 1 hour, and 200°C for 1 hour to obtain a transesterification product;

(2) Add 0.1g tetrabutyl titanate and 0.15g triethyl phosphite to the transesterified product obtained in step (1), polycondense for 3 hours at 250°C and high vacuum (≦133Pa) to obtain product.

After testing, the L, a, and b values of the product are 77, 3, and 4 respectively, the tensile strength is 42MPa, the elongation at break is 213%, and the impact strength is 4.8KJ/m ² .

Example 10

(1) Add 66.28g 2,5-dimethyl furandicarboxylate, 64.84g butylene glycol in the reactor of nitrogen atmosphere, 28.1g molecular weight is the polyethylene glycol of 1000g/mol and 0.17g stannous oxalate, at 170 ℃ for 1 hour, 180 ℃ for 1 hour, 190 ℃ for 1 hour, 200 ℃ for 1 hour to obtain the transesterification product;

(2) Add 0.1 g of lithium acetylacetonate to the transesterified product obtained in step (1), and conduct polycondensation at 240° C. and high vacuum (≦133 Pa) for 3 hours to obtain the product.

After testing, the L, a, and b values of the product are 77, 3, and 2 respectively, the tensile strength of the product is 46MPa, the elongation at break is 271%, and the impact strength is 29.7KJ/m ² .

Example 11

(1) Add 61.93g dimethyl 2,5-furandicarboxylate, 31.27g ethylene glycol, 20g 2,2,4,4-tetramethyl-1,3-cyclobutanedi Alcohol, 20.4g of polytetramethylene glycol with a molecular weight of 2000g/mol and 0.1g of isopropyl titanate were reacted at 170°C for 1 hour, 180°C for 1 hour, 190°C for 1 hour, and 200°C for 1 hour to obtain a transesterification product ;

(2) Add 0.05 g of tetrabutyl titanate and 2.4 g of nano-talc powder to the transesterification product obtained in step (1), and polycondense at 240° C. for 3 hours under high vacuum (≦133 Pa) to obtain the product.

After testing, the L, a, and b values of the product are 75, 3, and 4 respectively, the tensile strength of the product is 67MPa, the elongation at break is 127%, and the impact strength is 2.4KJ/m ² .

Example 12

(1) Add 66.28g 2,5-furandicarboxylic acid dimethyl ester, 42.87g propylene glycol in the reactor of nitrogen atmosphere, 25g 1,4-cyclohexanedimethanol, 35.6g molecular weight is the polypropylene glycol of 1000g/mol and 0.18g of silicon dioxide/titanium dioxide composite was reacted at 170°C for 1 hour, 180°C for 1 hour, 190°C for 1 hour, and 200°C for 1 hour to obtain a transesterification product;

(2) Add 0.07 g of antimony trioxide to the transesterification product obtained in step (1), and polycondense for 4 hours at 245° C. and high vacuum (≦133 Pa) to obtain the product.

After testing, the L, a, and b values of the product are 65, 3, and 7 respectively, the tensile strength of the product is 58MPa, the elongation at break is 117%, and the impact strength is 2.3KJ/m ² .

Example 13

(1) Add 67.49g 2,5-furandicarboxylic acid dimethyl ester, 30.56g butanediol, 35g 1,4-cyclohexanediol, 16.4g molecular weight to the reactor of nitrogen atmosphere and be 1000g/mol poly Butanediol, 0.1g tetrabutyl titanate and 2.1g nano-titanium dioxide were reacted at 170°C for 1 hour, 180°C for 1 hour, 190°C for 1 hour, and 200°C for 1 hour to obtain a transesterification product;

(2) Add 0.16 g of titanium ethylene glycol to the transesterification product obtained in step (1), and conduct polycondensation at 230° C. and high vacuum (≦133 Pa) for 5 hours to obtain the product.

After testing, the L, a, and b values of the product are 68, 3, and 8 respectively, the tensile strength of the product is 42MPa, the elongation at break is 277%, and the impact strength is 10.8KJ/m ² .

Example 14

(1) Add 64.83g 2,5-dimethyl furandicarboxylate, 48.35g ethylene glycol in the reactor of nitrogen atmosphere, 26.4g molecular weight is the polyisobutylene glycol of 1000g/mol and 0.1g tetrabutyl titanate, React at 170°C for 1 hour, 180°C for 1 hour, 190°C for 1 hour, and 200°C for 1 hour to obtain the transesterification product;

(2) Add 0.12 g of tetrabutyl titanate to the transesterified product obtained in step (1), and conduct polycondensation at 245° C. and high vacuum (≦133 Pa) for 3 hours to obtain the product.

After testing, the L, a, and b values of the product are 66, 3, and 6 respectively, the tensile strength of the product is 63MPa, the elongation at break is 107%, and the impact strength is 15.8KJ/m ² .

Example 15

(1) Add 64.38g 2,5-dimethyl furandicarboxylate, 67.84g butylene glycol in the reactor of nitrogen atmosphere, 14.4g molecular weight is the polyisobutylene glycol of 2000g/mol and 0.1g tetrabutyl titanate and 0.25g heat stabilizer 1010, react at 170°C for 1 hour, 180°C for 1 hour, 190°C for 1 hour, and 200°C for 1 hour to obtain an esterified product;

(2) Add 0.13 g of tetrabutyl titanate to the esterification product obtained in step (1), and conduct polycondensation at 240° C. and high vacuum (≦133 Pa) for 3 hours to obtain the product.

After testing, the L, a, and b values of the product are 76, 3, and 4 respectively, the tensile strength of the product is 47MPa, the elongation at break is 207%, and the impact strength is 11.4KJ/m ² .

Claims (10)

1. a kind of biological poly ester material, which is characterized in that including 2,5-furandicarboxylic acid binary alcohol esters hard section shown in formula (I) 2,5-furandicarboxylic acid binary alcohol esters soft segment unit shown in unit and formula (II),

R₁It is selected from-CH₂CH₂OCH₂CH₂-、 One or more of；

R₂It is selected fromOne or more of；

R₃Selected from-CH₂CH₂-、-CH₂CH₂CH₂-、-CH₂CH₂CH₂CH₂One or more of；

X is the integer of 2-4, and y is the integer of 4-70, and z is the integer of 5-55；

-R₂It is HO-R₂The residue of-OH, HO-R₂The molecular weight of-OH is 300-3000g/mol；

Wherein ,-R₂Segment accounts for the 1-35wt% of the biological poly ester material.

2. biological poly ester material according to claim 1, which is characterized in that R₂For

Wherein, the definition of y and z is as described in claim 1.

3. biological poly ester material according to claim 1, which is characterized in that according to Lab color model, the biology base Polyester material L value is that 60 or more, a value is 5 hereinafter, b value is 10 or less.

4. biological poly ester material according to claim 1, which is characterized in that the HO-R₂The molecular weight of-OH is 500- 2000g/mol。

5. biological poly ester material according to claim 1, which is characterized in that-R₂Segment accounts for the biology base polyester material The 1-20wt% of material.

6. biological poly ester material according to claim 1, which is characterized in that-R₂Segment accounts for the biology base polyester material The 20-35wt% of material.

7. biological poly ester material according to claim 1, which is characterized in that-R₂Segment accounts for the biology base polyester material The 33-35wt% of material.

8. the preparation method of described in any item biological poly ester materials according to claim 1~7, which is characterized in that it includes Following steps:

(1) under the action of catalyst A, monomer a, monomer b and monomer c carry out esterification/ester exchange reaction, and intermediate is made；

(2) intermediate that step (1) obtains is mixed with catalyst B, is heated up and is carried out depressurization condensation reaction to get the biology Base polyester material；

The monomer a is 2,5- furandicarboxylic acid, 2,5- furandicarboxylic acid diester or their mixture；Wherein, 2,5- furans Dicarboxylate is 2,5- furandicarboxylic acid dimethyl ester or 2,5- furandicarboxylic acid diethylester；

The monomer b be ethylene glycol, 1,3- propylene glycol, 1,4- butanediol, 1,4 cyclohexane dimethanol, 1,4- cyclohexane diol and One or more of 2,2,4,4- tetramethyl -1,3- cyclobutanediol；

The monomer c is one or more of polyethylene glycol, polypropylene glycol, polytetramethylene glycol and polyisobutene glycol.

9. the preparation method of biological poly ester material according to claim 8, which is characterized in that the catalyst A is titanium Sour N-butyl, isopropyl titanate, stannous octoate, stannous oxalate, Dibutyltin oxide, lithium acetate, potassium acetate, calcium acetate, acetic acid Magnesium, barium acetate, zinc acetate, cobalt acetate, antimony acetate, lead acetate, manganese acetate, the compound of earth silicon/titanic oxide, titanium dioxide One of silicon/titanium dioxide/nitrogenous compound compound and earth silicon/titanic oxide/phosphorus-containing compound compound Or it is several；

And/or the dosage of the catalyst A is 0.005~0.5mol% that monomer a adds mole；

And/or the catalyst B is tetrabutyl titanate, isopropyl titanate, titanium ethylene glycolate, titanium acetylacetone, antimony glycol, three Aoxidize two antimony, antimony acetate, zinc acetate, manganese acetate, lead acetate, calcium acetate, cobalt acetate, potassium acetate, magnesium acetate, barium acetate, acetic acid Lithium, the compound of earth silicon/titanic oxide, earth silicon/titanic oxide/nitrogenous compound compound and silica/ One or more of titanium dioxide/phosphorus-containing compound compound；

And/or the dosage of the catalyst B is 0.005~0.5mol% that monomer a adds mole in step (1)；

And/or auxiliary agent is added in step (1) or (2), the auxiliary agent is in heat stabilizer, light stabilizer and inorganic filler One or more, the dosage of the auxiliary agent are 0.1~20wt% that monomer a adds quality；

And/or in step (1), the molar ratio of monomer b and monomer a are 1.1~3:1；The dosage of monomer c accounts for monomer a and monomer c 0.5~50wt% of total mass fraction.

And/or in step (1), the temperature of the esterification/ester exchange reaction is 170~210 DEG C, reaction, and the time is 1~10h；

And/or in step (2), the temperature of the depressurization condensation reaction is 210~260 DEG C, system pressure≤200Pa, when polycondensation Between be 1~8h.

10. a kind of application of biological poly ester materials described in any item according to claim 1~7, which is characterized in that the life Object base polyester material is used as one of packaging material, medical material, fiber and engineering plastics or a variety of.