CN110229480B - Preparation method of polybutylene furan dicarboxylate and polybutylene terephthalate blend - Google Patents
Preparation method of polybutylene furan dicarboxylate and polybutylene terephthalate blend Download PDFInfo
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- CN110229480B CN110229480B CN201910618513.1A CN201910618513A CN110229480B CN 110229480 B CN110229480 B CN 110229480B CN 201910618513 A CN201910618513 A CN 201910618513A CN 110229480 B CN110229480 B CN 110229480B
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
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- C08L2201/14—Gas barrier composition
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- C08L2203/10—Applications used for bottles
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L2203/16—Applications used for films
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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Abstract
The application discloses a preparation method of a blend of poly (2, 5-furandicarboxylic acid-1, 4-butanediol ester) and poly (terephthalic acid-1, 4-butanediol ester), which comprises the following steps: the mixture containing poly-1, 4-butanediol 2, 5-furandicarboxylate and poly-1, 4-butanediol terephthalate is subjected to melt blending to obtain the poly-1, 4-butanediol 2, 5-furandicarboxylate and poly-1, 4-butanediol terephthalate blend. The blend reduces the melting point of the poly (1, 4-butylene terephthalate), and the lower melting point is beneficial to reducing the synthesis and processing temperature and reducing the energy consumption, thereby further obtaining the bio-based blend with high gas barrier property. Therefore, the copolyester material can better meet the application requirements of the copolyester material in the fields of food packaging, medicine packaging, automobiles, electronics and the like.
Description
Technical Field
The invention relates to a preparation method of a blend of poly-2, 5-furandicarboxylic acid-1, 4-butanediol ester and poly-terephthalic acid-1, 4-butanediol ester, wherein the prepared blend of poly-2, 5-furandicarboxylic acid-1, 4-butanediol ester and poly-terephthalic acid-1, 4-butanediol ester is prepared into a polyester structural member, a barrier film and a barrier bottle which are used in the fields of food packaging, medicine packaging, automobiles, electronics and the like.
Background
At present, the bio-based polymer materials widely used mainly include polylactic acid (PLA), Polyhydroxyalkanoate (PHA), polyglycolic acid (PGA), polybutylene succinate (PBS), and the like. They all belong to aliphatic polymers, and because of lack of rigid aromatic ring structure in the molecular structure, the mechanical properties (such as strength, modulus, creep resistance and the like) and heat resistance (such as thermal mechanical properties, thermal deformation temperature and the like) of the aliphatic polymers are obviously lower than petroleum-based high polymer materials such as polyethylene terephthalate (PET), Polycarbonate (PC), aromatic nylon (PA), bisphenol A type Epoxy resin (Epoxy) and the like, and the application range of the aliphatic polymers is severely limited. The molecular structure of 2, 5-furandicarboxylic acid (2,5-FDCA) contains aromatic rings, and the aromatic rings are used for synthesizing a bio-based polymer material, so that the heat resistance and the mechanical property of the material can be effectively improved, and simultaneously, the oxygen and carbon dioxide barrier property of the 1, 4-butanediol polyfurandicarboxylate can be improved by 3-5 times compared with that of the 1, 4-butanediol polyterephthalate, so that the gas barrier property and the bio-based content of the 1, 4-butanediol polyterephthalate can be effectively improved by adding the 1, 4-butanediol polyfurandicarboxylate into the 1, 4-butanediol polyterephthalate.
Disclosure of Invention
According to one aspect of the present application, a method of making a high molecular weight, high gas barrier biobased blend is provided. In the preparation method, poly-2, 5-furandicarboxylic acid-1, 4-butanediol ester and poly-terephthalic acid-1, 4-butanediol ester are blended to form a blend of poly-2, 5-furandicarboxylic acid-1, 4-butanediol ester and poly-terephthalic acid-1, 4-butanediol ester, so that the melting point of the poly-terephthalic acid-1, 4-butanediol ester is reduced to a certain extent, the lower melting point is favorable for reducing the synthesis and processing temperature, the energy consumption is reduced, and the bio-based blend with high gas barrier property is further obtained. Therefore, the copolyester material can better meet the application requirements of the copolyester material in the fields of food packaging, medicine packaging, automobiles, electronics and the like.
The preparation method of the blend of the poly-1, 4-butanediol 2, 5-furandicarboxylate and the poly-1, 4-butanediol terephthalate comprises the following steps:
the mixture containing poly-1, 4-butanediol 2, 5-furandicarboxylate and poly-1, 4-butanediol terephthalate is subjected to melt blending to obtain the poly-1, 4-butanediol 2, 5-furandicarboxylate and poly-1, 4-butanediol terephthalate blend.
Optionally, the mass ratio of the poly-1, 4-butanediol 2, 5-furandicarboxylate to the poly-1, 4-butanediol terephthalate in the mixture containing poly-1, 4-butanediol 2, 5-furandicarboxylate and poly-1, 4-butanediol terephthalate is 0.01-0.99: 0.99-0.01.
Optionally, the mass ratio of poly-1, 4-furandicarboxylate to poly-1, 4-butylene terephthalate in the mixture comprising poly-1, 4-furandicarboxylate and poly-1, 4-butylene terephthalate is in a range between 1:9, 2:8, 3:7, 4:6, 6:4, 7:3, 8:2, 9:1, and any two ratios thereof.
Optionally, the intrinsic viscosity of the poly-1, 4-butanediol-2, 5-furandicarboxylate and poly-1, 4-butanediol terephthalate blend is from 0.75 to 1.20 dL/g.
Optionally, the upper limit of the intrinsic viscosity of the poly-1, 4-furandicarboxylic acid-1, 4-butanediol terephthalate and poly-1, 4-butanediol ester blend is selected from the group consisting of 0.75dL/g, 0.83dL/g, 0.88dL/g, 0.93dL/g, 0.95dL/g, 1.05dL/g, 1.06dL/g, 1.10dL/g, 1.17dL/g, 1.20dL/g, and a range value between any two values thereof.
Optionally, the blend of poly-1, 4-butanediol-2, 5-furandicarboxylate and poly-1, 4-butanediol terephthalate has a carbon dioxide gas barrier property of 1.1 × 10-12cm3·cm/cm2·s·cmHg-1.8×10-11cm3·cm/cm2·s·cmHg。
Alternatively, the blend of poly-1, 4-butanediol-2, 5-furandicarboxylate and poly-1, 4-butanediol terephthalate has an oxygen gas barrier property of 1.8 x 10-12cm3·cm/cm2·s·cmHg-.2×10-12cm3·cm/cm2·s·cmHg。
Optionally, the poly-1, 4-butanediol 2, 5-furandicarboxylate has an intrinsic viscosity of 0.45 to 0.90 dL/g.
Optionally, the intrinsic viscosity of the poly (1, 4-butanediol terephthalate) blend is from 0.45 to 0.90 dL/g.
Optionally, the mixture containing poly-1, 4-butylene 2, 5-furandicarboxylate and poly-1, 4-butylene terephthalate further comprises an auxiliary agent;
the auxiliary agent comprises at least one of color masterbatch, anti-ultraviolet auxiliary agent, crystallization nucleating agent, antioxidant and stabilizer.
Optionally, the stabilizer is selected from at least one of phosphoric acid, phosphorous acid, hypophosphorous acid, pyrophosphoric acid, ammonium phosphate, trimethyl phosphate, dimethyl phosphate, triphenyl phosphate, diphenyl phosphate, triphenyl phosphite, diphenyl phosphite, ammonium phosphite, and ammonium dihydrogen phosphate;
the mass of the stabilizer is 0.05-0.3% of the total mass of the blend of the poly-2, 5-furandicarboxylic acid-1, 4-butanediol ester and the poly-terephthalic acid-1, 4-butanediol ester.
Optionally, the antioxidant comprises a phenolic antioxidant;
the mass of the antioxidant is 0.05-0.5% of the total mass of the blend of the poly-2, 5-furandicarboxylic acid-1, 4-butanediol ester and the poly-terephthalic acid-1, 4-butanediol ester.
Optionally, the antioxidant is selected from at least one of antioxidant-1010, antioxidant-1076, and antioxidant-168.
Optionally, the melt blending temperature is from 220 ℃ to 260 ℃.
Optionally, the upper limit of the temperature of the melt blending is selected from 225 ℃, 230 ℃, 235 ℃, 240 ℃, 245 ℃, 250 ℃, 255 ℃ or 260 ℃; the lower limit is selected from 220 deg.C, 225 deg.C, 230 deg.C, 235 deg.C, 240 deg.C, 245 deg.C, 250 deg.C or 255 deg.C.
Alternatively, the melt blending comprises extrusion melt blending, or autoclave melt blending.
Optionally, the melt blending of the reaction kettle is carried out under the vacuum condition of 3-200 Pa, and the melt blending time of the reaction kettle is 0.5-6 hours.
Alternatively, the extrusion melt blending comprises single screw extrusion melt blending, twin screw extrusion melt blending;
the rotating speed of the screw for extruding and melt blending is 20 rpm-30 rpm.
Optionally, the extrusion melt blending comprises no less than six temperature zones;
the temperatures of the six temperature zones are all 220-260 ℃, and the temperature of the latter temperature zone is not lower than that of the former temperature zone.
According to another aspect of the present application, there is provided an article comprising a blend of poly-1, 4-butanediol-2, 5-furandicarboxylate and poly-1, 4-butanediol terephthalate prepared according to the method of preparing a blend of poly-1, 4-butanediol-2, 5-furandicarboxylate and poly-1, 4-butanediol terephthalate.
According to another aspect of the present application, there is provided a member comprising a blend of poly-1, 4-butylene 2, 5-furandicarboxylate and poly-1, 4-butanediol terephthalate prepared according to the method of preparing a blend of poly-1, 4-butylene 2, 5-furandicarboxylate and poly-1, 4-butanediol terephthalate.
According to another aspect of the present application, there is provided a barrier film comprising a blend of poly-1, 4-butanediol-2, 5-furandicarboxylate and poly-1, 4-butanediol terephthalate prepared according to the method of preparing a blend of poly-1, 4-butanediol-2, 5-furandicarboxylate and poly-1, 4-butanediol terephthalate.
According to another aspect of the present application, there is provided a barrier bottle comprising a blend of poly-1, 4-butanediol-2, 5-furandicarboxylate and poly-1, 4-butanediol terephthalate prepared according to the method of preparing a blend of poly-1, 4-butanediol-2, 5-furandicarboxylate and poly-1, 4-butanediol terephthalate.
According to still another aspect of the present application, there is provided the use of the article, the member, the barrier film, the barrier bottle in the packaging, automotive, electronic fields.
According to yet another aspect of the application, there is provided the use of the article, the member, the barrier film, the barrier bottle in food packaging, pharmaceutical packaging.
The beneficial effects that this application can produce include:
1) the preparation method of the poly-2, 5-furandicarboxylic acid-1, 4-butanediol ester and poly-1, 4-butanediol terephthalate blend can effectively introduce the poly-1, 4-butanediol furan dicarboxylate structural unit into the poly-1, 4-butanediol terephthalate structure through melt blending to obtain the poly-1, 5-furandicarboxylic acid-1, 4-butanediol ester and poly-1, 4-butanediol terephthalate blend, compared with pure poly-1, 4-butanediol terephthalate, the blend has excellent oxygen and carbon dioxide barrier property, solves the problem that the gas barrier property of the current poly-1, 4-butanediol terephthalate is not good enough, can effectively improve the quality guarantee period of a packaged product, and simultaneously solves the problem that the gas barrier property of the current multilayer composite film such as oxygen is improved, but the material is difficult to recycle.
2) The poly-2, 5-furandicarboxylic acid-1, 4-butanediol ester and poly-1, 4-butanediol terephthalate blend prepared by the preparation method of the poly-2, 5-furandicarboxylic acid-1, 4-butanediol ester and poly-1, 4-butanediol terephthalate blend effectively utilizes the advantage of high gas barrier property of the poly-1, 4-butanediol furandicarboxylic acid, prepares the poly-1, 4-butanediol-2, 5-furandicarboxylic acid-1, 4-butanediol ester and poly-1, 4-butanediol terephthalate blend by melt blending, and solves the defects of high processing temperature and the like of the traditional poly-1, 4-butanediol terephthalate blend.
Drawings
FIG. 1 is a 1H-NMR spectrum of a blend of poly-1, 4-butanediol-2, 5-furandicarboxylate and poly-1, 4-butanediol terephthalate obtained in example 1.
FIG. 2 is a DSC chart of the blend of poly-1, 4-butylene-2, 5-furandicarboxylate and poly-1, 4-butylene terephthalate obtained in example 1.
Detailed Description
The invention is further illustrated by the following examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention.
In the examples, NMR spectra1H-NMR was measured on a Bruker 400 AVANCE III Spectrometer type instrument at 400MHz, CF3COOD。
In the examples, the intrinsic viscosity was measured by using phenol/tetrachloroethane (1:1m/m) as a solvent, and at 30. + -. 0.05 ℃ by using a Ubbelohde viscometer, and the intrinsic viscosity [. eta. ] of the polyester and the block copolyester was calculated according to the formulae (1), (2) and (3).
ηsp＝(t1-t0)/t0 (1)
[η]＝[(1+1.4ηsp)1/2-1]/0.7c (2)
Wherein: t is t0The flow time(s) of the solvent; t is t1The flow time(s) of the solution; c is the concentration of the solution, 5 g/L.
In the examples, thermal analysis (DSC) was carried out on a differential scanning calorimeter, N2Atmosphere, test scanning temperature-70-300 deg.c, 10 deg.c/min.
In the examples, the barrier properties against oxygen and carbon dioxide were measured by permeability testing using Labthink VAC-V2, each in CO2And O2As an air source, under the conditions of 23 ℃ and 50% RH of temperature and humidity respectively, the sample size phi of 97mm and the transmission area 38 are selected.5cm2。
In the examples, the preparation of poly-1, 4-butylene-2, 5-furandicarboxylate was as follows: 2, 5-furandicarboxylic acid and 1, 4-butanediol are used as raw materials and synthesized by a two-step melt polycondensation method. The intrinsic viscosity was measured to be 0.63dL/g by a Ubbelohde viscometer.
In the examples, the preparation of poly (1, 4-butylene terephthalate) was as follows: the compound is synthesized by taking terephthalic acid and 1, 4-butanediol as raw materials through a two-step melt polycondensation method. The intrinsic viscosity was measured to be 0.69dL/g by a Ubbelohde viscometer.
Example 1
Uniformly mixing poly-2, 5-furandicarboxylic acid-1, 4-butanediol ester, poly-terephthalic acid-1, 4-butanediol ester, triphenyl phosphate and antioxidant-1010 according to the mass ratio of 0.3:0.7:0.001:0.002, adding the mixture into a reaction kettle, slowly vacuumizing to 10-100Pa, heating to 245 ℃, and carrying out melt blending for 1.5h at the stirring speed of 30rpm to obtain the poly-2, 5-furandicarboxylic acid-1, 4-butanediol ester and poly-terephthalic acid-1, 4-butanediol ester blend.
From1As can be seen from the H-NMR spectrum, as shown in FIG. 1, 1.76ppm (1, 4-butanediol intermediate position CH on the 1, 4-butanediol Furanodicarboxylic acid-1, 4-butanediol segment)2S, 4H), 1.83ppm (1, 4-butanediol neutral CH on the 1, 4-butanediol terephthalate segment)2S, 4H), 4.29ppm (CH on 1, 4-butanediol close to the ester group)2S, 4H), 7.11ppm (CH, s, 2H on furan ring), 7.90ppm (CH, s, 4H on benzene ring), 11.35ppm (solvent peak, CF)3COOD). The detected substance structure is consistent with the structure of the mixture of poly 2, 5-furandicarboxylic acid-1, 4-butanediol ester and poly terephthalic acid-1, 4-butanediol ester.
From the DSC curves, it can be seen that two melting points, attributed to PBF and PBT, appear at 170 ℃ and 223 ℃, respectively, as shown in fig. 2.
The detection proves that the intrinsic viscosity of the mixture of the poly 2, 5-furandicarboxylic acid-1, 4-butanediol ester and the poly terephthalic acid-1, 4-butanediol ester is 1.05dL/g, and the carbon dioxide gas barrier property is 1.6 multiplied by 10-11cm3·cm/cm2s.cmHg, oxygen gas barrier property of 3.8X 10-12cm3·cm/cm2·s·cmHg。
Example 2
Uniformly mixing poly (2, 5-furandicarboxylic acid-1, 4-butanediol ester), poly (1, 4-butanediol terephthalate), ammonium phosphite and antioxidant-1010 according to the mass ratio of 0.6:0.4:0.002:0.005, adding the mixture into a reaction kettle, slowly vacuumizing to 10-200Pa, heating to 235 ℃, and carrying out melt blending for 1.0h at the stirring speed of 30rpm to obtain the blend of poly (2, 5-furandicarboxylic acid-1, 4-butanediol ester) and poly (1, 4-butanediol terephthalate).
The detection proves that the intrinsic viscosity of the obtained poly (1, 4-butylene 2, 5-furandicarboxylate) and poly (1, 4-butylene terephthalate) blend is 0.75dL/g, two melting points appear at 170 ℃ and 223 ℃ respectively, the two melting points belong to PBF and PBT, and the carbon dioxide gas barrier property is 1.8 multiplied by 10-11cm3·cm/cm2s.cmHg, oxygen gas barrier properties of 4.2X 10-12cm3·cm/cm2·s·cmHg。
Example 3
Uniformly mixing poly (2, 5-furandicarboxylic acid-1, 4-butanediol ester), poly (1, 4-butanediol terephthalate), ammonium dihydrogen phosphate and antioxidant-1010 according to a mass ratio of 0.8:0.2:0.005:0.001, adding the mixture into a reaction kettle, slowly vacuumizing to 15-100Pa, heating to 230 ℃, and carrying out melt blending for 1.0h at a stirring speed of 30rpm to obtain a poly (2, 5-furandicarboxylic acid-1, 4-butanediol ester) and poly (1, 4-butanediol terephthalate).
The detection proves that the intrinsic viscosity of the obtained poly (1, 4-butylene 2, 5-furandicarboxylate) and poly (1, 4-butylene terephthalate) blend is 0.93dL/g, two melting points appear at 172 ℃ and 222 ℃ respectively, the two melting points belong to PBF and PBT, and the carbon dioxide gas barrier property is 7.5 multiplied by 10-12cm3·cm/cm2s.cmHg, oxygen gas barrier property of 3.1X 10-12cm3·cm/cm2·s·cmHg。
Example 4
Uniformly mixing poly (2, 5-furandicarboxylic acid) -1, 4-butanediol ester, poly (1, 4-butanediol terephthalate), triphenyl phosphate and antioxidant-1010 according to the mass ratio of 0.3:0.7:0.001:0.002 for later use. The temperature of the double-screw extruder is set to be 220 ℃ in the first zone, 225 ℃ in the second zone, 225 ℃ in the third zone, 230 ℃ in the fourth zone, 235 ℃ in the fifth zone and 240 ℃ in the sixth zone, after the temperature is reached, the prepared mixture is added into a double-screw extrusion feeding port, and the mixture is extruded at the screw rotating speed of 25rpm to obtain the mixture of poly (2, 5-furandicarboxylic acid-1, 4-butanediol ester) and poly (terephthalic acid-1, 4-butanediol ester).
The detection proves that the intrinsic viscosity of the obtained poly (1, 4-butylene 2, 5-furandicarboxylate) and poly (1, 4-butylene terephthalate) blend is 0.95dL/g, two melting points appear at 170 ℃ and 223 ℃ respectively, the two melting points belong to PBF and PBT, and the carbon dioxide gas barrier property is 1.5 multiplied by 10-11cm3·cm/cm2s.cmHg, oxygen gas barrier property of 3.5X 10-12cm3·cm/cm2·s·cmHg。
Example 5
Uniformly mixing poly (2, 5-furandicarboxylic acid-1, 4-butylene glycol ester), poly (1, 4-butylene glycol terephthalate), triphenyl phosphate and antioxidant-1010 according to the mass ratio of 0.6:0.4:0.0015:0.0015 for later use. The temperature of the double-screw extruder is set to be 225 ℃ in the first zone, 225 ℃ in the second zone, 230 ℃ in the third zone, 230 ℃ in the fourth zone, 240 ℃ in the fifth zone and 240 ℃ in the sixth zone, after the temperature is reached, the prepared mixture is added into a double-screw extrusion feeding port, and the mixture is extruded at the screw rotating speed of 30rpm to obtain the mixture of poly (2, 5-furandicarboxylic acid-1, 4-butanediol ester) and poly (terephthalic acid-1, 4-butanediol ester).
The detection proves that the intrinsic viscosity of the obtained poly (1, 4-butylene 2, 5-furandicarboxylate) and poly (1, 4-butylene terephthalate) blend is 1.20dL/g, two melting points appear at 170 ℃ and 224 ℃ respectively, the two melting points belong to PBF and PBT, and the carbon dioxide gas barrier property is 8.3 multiplied by 10-12cm3·cm/cm2s.cmHg, oxygen gas barrier properties of 1.8X 10-12cm3·cm/cm2·s·cmHg。
Example 6
Uniformly mixing poly (2, 5-furandicarboxylic acid) -1, 4-butanediol ester, poly (1, 4-butanediol terephthalate), diphenyl phosphate and antioxidant-1076 according to the mass ratio of 0.2:0.8:0.002:0.002 for later use. The temperature of the double-screw extruder is set to 230 ℃ in the first zone, 235 ℃ in the second zone, 235 ℃ in the third zone, 240 ℃ in the fourth zone, 240 ℃ in the fifth zone and 245 ℃ in the sixth zone, after the temperature is reached, the prepared mixture is added into a double-screw extrusion feeding port, and the mixture is extruded at the screw rotating speed of 25rpm to obtain the mixture of poly (2, 5-furandicarboxylic acid-1, 4-butanediol ester) and poly (terephthalic acid-1, 4-butanediol ester).
The detection proves that the intrinsic viscosity of the obtained poly (1, 4-butylene 2, 5-furandicarboxylate) and poly (1, 4-butylene terephthalate) blend is 1.10dL/g, two melting points appear at 170 ℃ and 223 ℃ respectively, the two melting points belong to PBF and PBT, and the carbon dioxide gas barrier property is 1.5 multiplied by 10-11cm3·cm/cm2s.cmHg, oxygen gas barrier properties of 4.2X 10-12cm3·cm/cm2·s·cmHg。
Example 7
Uniformly mixing poly (2, 5-furandicarboxylic acid-1, 4-butylene glycol ester), poly (1, 4-butylene glycol terephthalate), triphenyl phosphate and antioxidant-1010 according to the mass ratio of 0.3:0.7:0.0005:0.005 for later use. The temperature of the single-screw extruder is set to be 225 ℃ in the first zone, 230 ℃ in the second zone, 235 ℃ in the third zone, 240 ℃ in the fourth zone and 245 ℃ in the fifth zone, after the temperature is reached, the prepared mixture is added into a single-screw extrusion feeding port, and the mixture is extruded at the screw rotating speed of 25rpm to obtain the mixture of poly (2, 5-furandicarboxylic acid-1, 4-butanediol ester) and poly (terephthalic acid-1, 4-butanediol ester).
The detection proves that the intrinsic viscosity of the obtained poly (1, 4-butylene 2, 5-furandicarboxylate) and poly (1, 4-butylene terephthalate) blend is 1.17dL/g, two melting points appear at 170 ℃ and 223 ℃ respectively, the two melting points belong to PBF and PBT, and the carbon dioxide gas barrier property is 1.8 multiplied by 10-12cm3·cm/cm2s.cmHg, oxygen gas barrier property of 3.9X 10-12cm3·cm/cm2·s·cmHg。
Example 8
Uniformly mixing poly (2, 5-furandicarboxylic acid-1, 4-butanediol ester), poly (1, 4-butanediol terephthalate), hypophosphorous acid and antioxidant-168 according to the mass ratio of 0.7:0.3:0.0015:0.0015 for later use. The temperature of the single-screw extruder is set to be 220 ℃ in the first zone, 225 ℃ in the second zone, 230 ℃ in the third zone, 235 ℃ in the fourth zone and 240 ℃ in the fifth zone, after the temperature is reached, the prepared mixture is added into a single-screw extrusion feeding port, and the mixture is extruded at the screw rotating speed of 25rpm to obtain the mixture of poly (2, 5-furandicarboxylic acid-1, 4-butanediol ester) and poly (terephthalic acid-1, 4-butanediol ester).
The detection proves that the intrinsic viscosity of the obtained poly (2, 5-furandicarboxylic acid-1, 4-butanediol ester) and poly (terephthalic acid-1, 4-butanediol ester) blend is 1.06dL/g, two melting points appear at 170 ℃ and 223 ℃ respectively, the two melting points belong to PBF and PBT, and the carbon dioxide gas barrier property is 9.1 multiplied by 10-12cm3·cm/cm2s.cmHg, oxygen gas barrier property of 3.2X 10-12cm3·cm/cm2·s·cmHg。
Example 9
Uniformly mixing poly (2, 5-furandicarboxylic acid-1, 4-butanediol ester), poly (1, 4-butanediol terephthalate), hypophosphorous acid and antioxidant-168 according to the mass ratio of 0.4:0.6:0.002:0.003 for later use. The temperature of the single-screw extruder is set to be 220 ℃ in the first zone, 225 ℃ in the second zone, 225 ℃ in the third zone, 235 ℃ in the fourth zone and 240 ℃ in the fifth zone, after the temperature is reached, the prepared mixture is added into a single-screw extrusion feeding port, and the mixture is extruded at the screw rotating speed of 25rpm to obtain the mixture of poly (2, 5-furandicarboxylic acid-1, 4-butanediol ester) and poly (terephthalic acid-1, 4-butanediol ester).
The detection proves that the intrinsic viscosity of the obtained poly (1, 4-butylene 2, 5-furandicarboxylate) and poly (1, 4-butylene terephthalate) blend is 0.83dL/g, two melting points appear at 170 ℃ and 223 ℃ respectively, the two melting points belong to PBF and PBT, and the carbon dioxide gas barrier property is 5.9 multiplied by 10-12cm3·cm/cm2s.cmHg, oxygen gas barrier properties of 2.8X 10-12cm3·cm/cm2·s·cmHg。
Example 10
Uniformly mixing poly (2, 5-furandicarboxylic acid-1, 4-butanediol ester), poly (1, 4-butanediol terephthalate), hypophosphorous acid and antioxidant-168 according to the mass ratio of 0.9:0.1:0.002:0.003 for later use. The temperature of the single-screw extruder is set to be 220 ℃ in the first zone, 220 ℃ in the second zone, 220 ℃ in the third zone, 225 ℃ in the fourth zone and 230 ℃ in the fifth zone, after the temperature is reached, the prepared mixture is added into a single-screw extrusion feeding port and extruded at the screw rotating speed of 25rpm to obtain the blend of poly (2, 5-furandicarboxylic acid-1, 4-butanediol ester) and poly (terephthalic acid-1, 4-butanediol ester).
The detection proves that the intrinsic viscosity of the obtained poly (1, 4-butylene 2, 5-furandicarboxylate) and poly (1, 4-butylene terephthalate) blend is 0.88dL/g, two melting points appear at 172 ℃ and 222 ℃ respectively, the two melting points belong to PBF and PBT, and the carbon dioxide gas barrier property is 1.1 multiplied by 10-12cm3·cm/cm2s.cmHg, oxygen gas barrier properties of 2.2X 10-12cm3·cm/cm2·s·cmHg。
Example 11
Uniformly mixing poly (2, 5-furandicarboxylic acid-1, 4-butanediol ester), poly (1, 4-butanediol terephthalate), triphenyl phosphate and antioxidant-1010 according to the mass ratio of 0.01:0.99:0.001:0.002, adding the mixture into a reaction kettle, slowly vacuumizing to 10-100Pa, heating to 250 ℃, and carrying out melt blending for 1.0h at the stirring speed of 30rpm to obtain the blend of poly (2, 5-furandicarboxylic acid-1, 4-butanediol ester) and poly (1, 4-butanediol terephthalate).
The detection proves that the intrinsic viscosity of the mixture of the poly 2, 5-furandicarboxylic acid-1, 4-butanediol ester and the poly terephthalic acid-1, 4-butanediol ester is 0.95dL/g, the melting point appears at 172 ℃, and the carbon dioxide gas barrier property is 1.9 multiplied by 10-11cm3·cm/cm2s.cmHg, oxygen gas barrier properties of 4.4X 10-12cm3·cm/cm2·s·cmHg。
Example 12
Uniformly mixing poly (2, 5-furandicarboxylic acid-1, 4-butanediol ester), poly (1, 4-butanediol terephthalate), triphenyl phosphate and antioxidant-1010 according to the mass ratio of 0.99:0.01:0.001:0.002, adding the mixture into a reaction kettle, slowly vacuumizing to 10-100Pa, heating to 225 ℃, and carrying out melt blending for 1.0h at the stirring speed of 30rpm to obtain the blend of poly (2, 5-furandicarboxylic acid-1, 4-butanediol ester) and poly (1, 4-butanediol terephthalate).
The detection proves that the intrinsic viscosity of the mixture of the poly 2, 5-furandicarboxylic acid-1, 4-butanediol ester and the poly terephthalic acid-1, 4-butanediol ester is 0.88dL/g, the melting point appears at 225 ℃, and the carbon dioxide gas barrier property is 1.5 multiplied by 10-12cm3·cm/cm2s.cmHg, oxygen gas barrier properties of 1.4X 10-12cm3·cm/cm2·s·cmHg。
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 (11)
1. A method for preparing a blend of poly (1, 4-butylene 2, 5-furandicarboxylate) and poly (1, 4-butylene terephthalate), comprising the steps of:
melt blending a mixture containing poly-2, 5-furandicarboxylic acid-1, 4-butanediol ester and poly-terephthalic acid-1, 4-butanediol ester to obtain a blend of the poly-2, 5-furandicarboxylic acid-1, 4-butanediol ester and the poly-terephthalic acid-1, 4-butanediol ester;
the mass ratio of the poly-2, 5-furandicarboxylic acid-1, 4-butanediol ester to the poly-1, 4-butanediol terephthalate in the mixture containing the poly-2, 5-furandicarboxylic acid-1, 4-butanediol ester and the poly-1, 4-butanediol terephthalate is 1-9: 9-1;
the melt blending comprises extrusion melt blending and reaction kettle melt blending;
the melting and blending of the reaction kettle are carried out under the vacuum condition of 3-200 Pa, and the melting and blending time of the reaction kettle is 0.5-6 hours;
the extrusion melt blending comprises single-screw extrusion melt blending and double-screw extrusion melt blending;
the rotating speed of the screw for extruding, melting and blending is 20-30 rpm;
the extrusion melt blending comprises no less than six temperature zones;
the temperatures of the six temperature zones are all 220-260 ℃, and the temperature of the latter temperature zone is not lower than that of the former temperature zone.
2. The method of claim 1, 5-furandicarboxylic acid-1, 4-butanediol and poly (1, 4-butanediol terephthalate) blend, wherein the intrinsic viscosity of the poly (2, 5-furandicarboxylic acid-1, 4-butanediol) and poly (1, 4-butanediol terephthalate) blend is 0.75-1.20 dL/g.
3. The method for preparing a poly-1, 4-butylene-2, 5-furandicarboxylate and poly-1, 4-butanediol terephthalate blend according to claim 1, wherein the mixture containing poly-1, 4-butylene-2, 5-furandicarboxylate and poly-1, 4-butylene terephthalate further comprises an auxiliary agent;
the auxiliary agent comprises at least one of color masterbatch, anti-ultraviolet auxiliary agent, crystallization nucleating agent, antioxidant and stabilizer.
4. The method for preparing a poly-1, 4-butylene-2, 5-furandicarboxylate and poly-1, 4-butylene-terephthalate blend according to claim 3, wherein the stabilizer is at least one selected from phosphoric acid, phosphorous acid, hypophosphorous acid, pyrophosphoric acid, ammonium phosphate, trimethyl phosphate, dimethyl phosphate, triphenyl phosphate, diphenyl phosphate, triphenyl phosphite, diphenyl phosphite, ammonium dihydrogen phosphate;
the mass of the stabilizer is 0.05-0.3% of the total mass of the blend of the poly-2, 5-furandicarboxylic acid-1, 4-butanediol ester and the poly-terephthalic acid-1, 4-butanediol ester.
5. The method of preparing a poly-1, 4-butylene-2, 5-furandicarboxylate and poly-1, 4-butanediol terephthalate blend of claim 3, wherein the antioxidant comprises a phenolic antioxidant;
the mass of the antioxidant is 0.05-0.5% of the total mass of the blend of the poly-2, 5-furandicarboxylic acid-1, 4-butanediol ester and the poly-terephthalic acid-1, 4-butanediol ester.
6. The method of claim 5, wherein the antioxidant is at least one selected from the group consisting of antioxidant-1010, antioxidant-1076, and antioxidant-168.
7. An article comprising a poly-1, 4-butanediol-2, 5-furandicarboxylate and poly-1, 4-butanediol terephthalate blend produced according to the process for producing a poly-1, 4-butanediol-2, 5-furandicarboxylate and poly-1, 4-butanediol terephthalate blend of any of claims 1 to 6.
8. A member comprising a poly-1, 4-butylene 2, 5-furandicarboxylate and poly-1, 4-butanediol terephthalate blend produced according to the method of producing a poly-1, 4-butylene 2, 5-furandicarboxylate and poly-1, 4-butanediol terephthalate blend of any one of claims 1 to 6.
9. A barrier film comprising a poly-1, 4-butylene 2, 5-furandicarboxylate and poly-1, 4-butanediol terephthalate blend produced according to the method of producing a poly-1, 4-butanediol 2, 5-furandicarboxylate and poly-1, 4-butanediol terephthalate blend of any of claims 1 to 6.
10. A barrier bottle comprising a poly-1, 4-butylene 2, 5-furandicarboxylate and poly-1, 4-butanediol terephthalate blend produced according to the process for producing a poly-1, 4-butylene 2, 5-furandicarboxylate and poly-1, 4-butanediol terephthalate blend of any of claims 1 to 6.
11. Use of the article of claim 7, the member of claim 8, the barrier film of claim 9, the barrier bottle of claim 10 in packaging, automotive, electronics.
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