CN116178688A - High-barrier PBCT/PBAT alloy material, blow molding product thereof and processing method thereof - Google Patents
High-barrier PBCT/PBAT alloy material, blow molding product thereof and processing method thereof Download PDFInfo
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Abstract
The invention discloses a rapid preparation method of a poly (terephthalic acid) -butylene carbonate (PBCT) and poly (terephthalic acid) -adipic acid-butylene terephthalate (PBAT) alloy material, and a series of high-barrier alloy materials with good light transmittance, good mechanical property and easy processing are obtained through single screw blow molding processing. The method blends PBCT and PBAT without adding any blending compatilizer, and can realize the rapid reactive compatibility of two phases under the action of the residual transesterification catalyst in the system during melt polycondensation. By adjusting the mole ratio of the aromatic polyester in the PBCT and the components of the PBCT in the alloy, the accurate regulation and control of the material with ideal performance is realized. The blending method can remarkably improve the comprehensive performance of the PBAT, and has important significance for the development of novel packaging materials.
Description
Technical Field
The invention belongs to the field of biomass degradation, and particularly relates to a reactive compatible high-barrier PBCT/PBAT alloy material, a blow molding product thereof and a processing method thereof.
Background
The polymer material has the characteristics of light weight, insulation, corrosion resistance, friction resistance, easy processing, low price and the like, and has various kinds and different performances, so the polymer material has wide application in various aspects from high-precision technologies such as aerospace and the like to civil products and the like. However, the non-degradability of the polymer material brings great convenience to human life and also brings great pressure to the ecological environment, and the development of environment-friendly degradable plastics becomes a critical problem to be solved urgently by all chemical enterprises.
Poly (terephthalic acid) -adipic acid-butanediol ester (PBAT) is taken as a typical aromatic-aliphatic degradable polyester, is now a key chemical which is hot and can be used for obtaining blowout type productivity, and creates huge market benefits. However, the aliphatic repeat chain segment in the main chain repeat unit of the PBAT is longer, so that the modulus and the strength of the PBAT are lower, and the application of the PBAT in the fields of food packaging, agricultural mulching films and the like is limited. Poly (terephthalic acid) -butylene carbonate (PBCT) is an emerging aromatic-aliphatic polyester, adipic acid in the main chain structure of PBAT is replaced by renewable resource dimethyl carbonate, and the aliphatic structure in the main chain repeating unit is reduced, so that the strength and modulus of the PBCT are improved to a certain extent compared with those of the PBAT. In addition, the higher ester group density of PBCT can further optimize the barrier properties of PBAT.
Compared with copolymerization modification, melt blending modification has the advantages of convenience, rapidness, adjustable performance and the like, but phase separation is very easy to occur due to the difference of blend compatibility during multiphase melt blending, and a large number of defect points are formed by agglomeration in a matrix, so that the performance of the alloy material is not increased and reduced. It is therefore often necessary to add additional blending compatibilizers in multiphase melt blending to optimize the blend compatibility. However, taking alloy materials such as PBAT/PLA or PBAT/PBST as an example, the blending compatibility is still poor after the blending compatilizer is added, the phase separation phenomenon is obvious, and the service performance of the product is reduced. How to solve the problem of poor blending compatibility of the PBAT alloy material, and has important significance for expanding the industrialized application of the PBAT.
Disclosure of Invention
Aiming at the technical problems, the invention provides a preparation method of a high-barrier PBCT/PBAT alloy material compatible with the reactivity of poly (terephthalic acid-adipic acid-butanediol ester) (PBAT), which can realize rapid reactive compatibility under the action of catalytic transesterification of a melt polycondensation residual catalyst by utilizing the terminal ester group of poly (terephthalic acid-carbonic acid-butanediol ester) (PBCT) and the terminal hydroxyl group of PBAT. The performance of the alloy material is regulated and controlled by regulating and controlling the content of aromatic groups in PBCT. And (3) performing blow molding film formation on the prepared PBCT/PBAT alloy material to obtain a series of degradable blow molding products with good performance. The invention can fundamentally solve the defect of poor blending compatibility of the PBAT alloy material, and has important significance for expanding the industrial application of PBAT.
The invention aims to provide a reactive compatible high-barrier PBCT/PBAT alloy material and a rapid preparation method, which are used for solving the technical problems of low strength, low modulus, poor barrier property, poor alloy material blending compatibility and the like of the PBAT proposed in the background art.
The second purpose of the invention is to provide a preparation method of the performance-controllable PBCT/PBAT alloy material blow molding product.
In order to achieve the above purpose, the present invention provides the following technical solutions:
in a first aspect, the invention discloses a reactive compatible high barrier PBCT/PBAT alloy material having a structure represented by the formula:
wherein m, n, x, y is a natural number and has a value range of 20-300;
m represents the number of repeating units of an aromatic segment (butylene terephthalate segment) in PBCT in the alloy material main chain; n represents the number of repeating units of an aliphatic segment (butylene carbonate segment) of PBCT in the alloy material main chain; x represents the number of repeating units of an aliphatic segment (butylene adipate segment) of PBAT in the alloy material main chain, and y represents the number of repeating units of an aromatic segment (butylene terephthalate segment) of PBAT in the alloy material main chain.
Further, the intrinsic viscosity of the high-barrier PBCT/PBAT alloy material is 1.0-2.0 dL/g, the number average molecular weight is 50-100 kg/mol, the glass transition temperature is-30-44 ℃, the melting temperature is 117-230 ℃, and the melt index is 3.0-20 g/10min.
Further, the weight percentage of the PBCT in the high-barrier PBCT/PBAT alloy material is 1-99%, and the rest is PBAT.
Further, the number of the aromatic chain segments in the PBCT accounts for 1-99% of the total number of the aliphatic chain segments and the aromatic chain segments in the PBCT, and the balance is the aliphatic chain segments; the number of the aromatic chain segments in the PBAT accounts for 47% of the total number of the aliphatic chain segments and the aromatic chain segments in the PBAT, and the balance is the aliphatic chain segments.
Further, the weight percentage of the PBCT in the high-barrier PBCT/PBAT alloy material is 20-80%.
Further, the weight percentage of PBCT in the high-barrier PBCT/PBAT alloy material is 50-60%.
Further, the number of the aromatic chain segments in the PBCT accounts for 40-60% of the total number of the aliphatic chain segments and the aromatic chain segments in the PBCT, and the balance is the aliphatic chain segments.
Further, the aromatic chain segments in the PBCT account for 49-58% of the total number of aliphatic chain segments and aromatic chain segments in the PBCT, and the balance is aliphatic chain segments.
In a second aspect, a preparation method of a high-barrier PBCT/PBAT alloy material is provided, and the preparation method comprises the following steps:
(1) Fully mixing PBCT and PBAT according to a certain proportion to obtain a premix;
(2) Extruding and granulating the premix by a double-screw extruder, wherein the temperature of the double-screw extruder is 160-260 ℃ and the rotating speed is 10-30 Hz; the feeding speed is 1.0-5.0 Hz, and the extruded melt is subjected to water cooling, drafting, air drying and granulating to obtain the PBCT/PBAT alloy material.
Further, the obtained PBCT/PBAT alloy material was dried in a vacuum oven at 60 ℃ for 24 hours to remove moisture.
Further, the mass ratio of the PBCT to the PBAT is 1:99-99:1.
Further, the mass ratio of the PBCT to the PBAT is 1:4-4:1.
Further, the number of the aromatic chain segments in the PBCT accounts for 1-99% of the total number of the aliphatic chain segments and the aromatic chain segments in the PBCT in terms of mole percent, and the balance is the aliphatic chain segments.
Further, the number of the aromatic chain segments in the PBAT is 47% of the total number of the aliphatic chain segments and the aromatic chain segments in the PBAT, and the balance is the aliphatic chain segments.
In a third aspect, a processing method of a high-barrier PBCT/PBAT alloy material blow molding product is provided, the dried alloy material is put into a single screw melt extrusion film blowing machine, the temperature of a charging section, a plasticizing section and a discharging hole template are respectively set to 160-240 ℃, 170-250 ℃, 180-260 ℃, the rotation speed of a host machine is 10-30 Hz, and the feeding rotation speed is 1.0-5.0 Hz in the blow molding process; the film is formed by air cooling, drawing and blow molding, the drawing ratio is 20-80, and the thickness of the finally obtained PBCT/PBAT alloy material film is 10-35 mu m.
Further, the temperatures of the feeding section, the plasticizing section and the discharging hole template of the single screw extrusion film blowing machine are 180-240 ℃, 190-250 ℃, 200-260 ℃, the rotating speed of the main machine is 20Hz, and the feeding rotating speed is 2.0Hz.
Further, the PBAT in the step (1) is KHB21AP11 or KHB21BP11 of China Conhui New Material Co., ltd, BASF of Germany
At least one of Ecoworld, NZ, md.T.of Jin Huizhao, china.
The beneficial effects are that:
the invention aims at rapidly preparing the PBCT/PBAT alloy material with controllable performance by utilizing a reactive compatibility mechanism. The aromatic-aliphatic polyester PBCT which is blocked by ester groups and the aromatic-aliphatic polyester PBAT which is blocked by hydroxyl groups are directly subjected to melt blending, and the PBCT/PBAT alloy material with perfect compatibility is obtained on the premise of not adding any blending compatilizer. Wherein: by regulating and controlling the proportion of the aromatic chain segments in the PBCT, the strength, toughness, heat resistance, barrier property and the like of the PBAT can be regulated and controlled, and further, the accurate synthesis of the PBCT/PBAT alloy material with ideal properties is realized.
Drawings
FIG. 1 shows a PBCT/PBAT alloy material obtained in example 1 of the present invention 1 H-NMR spectrum;
FIG. 2 is a DSC spectrum of a PBCT/PBAT alloy material obtained in example 1 of the present invention;
FIG. 3 is a blow molded article of the PBCT/PBAT alloy material obtained in example 1 of the present invention.
Detailed Description
The present invention will be further illustrated with reference to the following specific examples, but the present invention should not be limited to the following examples.
The intrinsic viscosity, molecular weight, thermal properties, melt index and water blocking properties of the following examples were all determined as follows:
intrinsic viscosity: 0.2g of PBCT/PBAT alloy material is dissolved in 20 ml of mixed solution of phenol-1, 2-tetrachloroethane with the mass ratio of 1:1, and the calculation formula of the intrinsic viscosity is:
wherein: η (eta) r : relative viscosity, eta sp : increasing specific viscosity, t 0 : solvent run-off time, t 1 : polymer solution run-off time, c: polymer solution concentration.
Molecular weight: gel Permeation Chromatograph (GPC), using chloroform as solvent, monodisperse polystyrene as standard;
thermal performance: characterized by a Differential Scanning Calorimeter (DSC);
melt index: based on national standards GBT3682.1 and 3682.2, characterized by a melt index tester;
water blocking performance: based on the international standard ISO15106-2:2003, characterized by a water vapor transmission tester.
Example 1. Rapid preparation of reactive compatible high barrier PBCT/PBAT alloy Material and method of processing blow molded articles
(1) 500g of self-made PBCT with 58% of aromatic content and 500g of commercial PBAT are fully mixed, and are added into a double-screw extruder, the processing temperature from a feed inlet of the double-screw extruder to a die head is 180 ℃,182 ℃,185 ℃,187 ℃,190 ℃ and 180 ℃, the rotating speed of a main machine is 25Hz, the rotating speed of a feeding machine is 4.0Hz, and the PBCT/PBAT alloy material is obtained after water cooling, granulating and drying, wherein: an intrinsic viscosity of 1.35dL/g, a number average molecular weight of 85.3kg/mol, a glass transition temperature of-16.5 ℃, a melting temperature of 133.8 ℃ and a melt index of 4.3g/10min;
(2) And then adding the dried alloy material into a single-screw extrusion film blowing machine, wherein the temperatures of a feeding section, a plasticizing section and a discharging hole template are respectively set at 180 ℃,190 ℃ and 192 ℃, and the rotating speed of a main machine is 20Hz and the feeding rotating speed is 2.0Hz in the blowing process. Film forming by air cooling, drawing and blow molding with a drawing ratio of 40, and the thickness of the final PBCT/PBAT alloy material film is 15-20 μm, and the water vapor permeability coefficient is 5.5X10 -14 g·cm/cm 2 ·s·Pa。
Example 2. Rapid preparation of reactive compatible high barrier PBCT/PBAT alloy Material and method of processing blow molded articles
(1) 500g of self-made PBCT with the aromatic content of 49% and 500g of commercial PBAT are fully mixed, and are added into a double-screw extruder, the processing temperature from a feed inlet of the double-screw extruder to a die head is 175 ℃,180 ℃,182 ℃,185 ℃,190 ℃ and 180 ℃, the rotating speed of a main machine is 25Hz, the rotating speed of a feeding machine is 4.0Hz, and the PBCT/PBAT alloy material is obtained after water cooling, granulating and drying, wherein: an intrinsic viscosity of 1.33dL/g, a number average molecular weight of 84.1kg/mol, a glass transition temperature of-18.2 ℃, a melting temperature of 124.2 ℃ and a melt index of 3.9g/10min;
(2) And then adding the dried alloy material into a single-screw extrusion film blowing machine, wherein the temperatures of a feeding section, a plasticizing section and a discharging hole template are respectively set at 170 ℃,180 ℃ and 182 ℃, and the rotating speed of a main machine is 20Hz and the feeding rotating speed is 2.0Hz in the blowing process. Film forming by air cooling, drawing and blow molding with a drawing ratio of 40, and the thickness of the final PBCT/PBAT alloy material film is 25-30 μm, and the water vapor permeability coefficient is 6.0X10 -14 g·cm/cm 2 ·s·Pa。
Example 3. Rapid preparation of reactive compatible high barrier PBCT/PBAT alloy Material and method of processing blow molded articles
(1) Fully mixing 200g of self-made PBCT with 49% of aromatic content with 800g of commercial PBAT, adding the mixture into a double-screw extruder, wherein the processing temperature from a feed inlet of the double-screw extruder to a die head is 175 ℃,180 ℃,182 ℃,185 ℃,190 ℃ and 180 ℃, the rotating speed of a main machine is 25Hz, the rotating speed of a feeding machine is 4.0Hz, and obtaining the PBCT/PBAT alloy material after water cooling, granulating and drying, wherein: an intrinsic viscosity of 1.40dL/g, a number average molecular weight of 90.2kg/mol, a glass transition temperature of-27.4 ℃, a melting temperature of 122.5 ℃ and a melt index of 2.6g/10min;
(2) And then adding the dried alloy material into a single-screw extrusion film blowing machine, wherein the temperatures of a feeding section, a plasticizing section and a discharging hole template are respectively set at 170 ℃,180 ℃ and 182 ℃, and the rotating speed of a main machine is 20Hz and the feeding rotating speed is 2.0Hz in the blowing process. Film forming by air cooling, drawing and blow molding with a drawing ratio of 40, and the thickness of the final PBCT/PBAT alloy material film is 20-25 μm, and the water vapor permeability coefficient is 9.1×10 -14 g·cm/cm 2 ·s·Pa。
Example 4. Rapid preparation of reactive compatible high barrier PBCT/PBAT alloy Material and method of processing blow molded articles
(1) Fully mixing 200g of self-made PBCT with 58% of aromatic content with 800g of commercial PBAT, adding the mixture into a double-screw extruder, wherein the processing temperature from a feed inlet of the double-screw extruder to a die head is 180 ℃,182 ℃,185 ℃,187 ℃,190 ℃ and 180 ℃, the rotating speed of a main machine is 25Hz, the rotating speed of a feeding machine is 4.0Hz, and obtaining the PBCT/PBAT alloy material after water cooling, granulating and drying, wherein: the intrinsic viscosity is 1.38dL/g, the number average molecular weight is 87.6kg/mol, the glass transition temperature is-27.8 ℃, the melting temperature is 127.3 ℃, and the melt index is 3.1g/10min;
(2) And then adding the dried alloy material into a single-screw extrusion film blowing machine, wherein the temperatures of a feeding section, a plasticizing section and a discharging hole template are respectively set at 180 ℃,190 ℃ and 192 ℃, and the rotating speed of a main machine is 20Hz and the feeding rotating speed is 2.0Hz in the blowing process. Film forming by air cooling, drawing and blow molding with a drawing ratio of 40, and the thickness of the final PBCT/PBAT alloy material film is 20-25 μm, and the water vapor permeability coefficient is 8.8X10 -14 g·cm/cm 2 ·s·Pa。
Example 5. Rapid preparation of reactive compatible high barrier PBCT/PBAT alloy Material and method of processing blow molded articles
(1) 800g of self-made PBCT with 49% aromatic content and 200g of commercial PBAT are fully mixed, and are added into a double-screw extruder, the processing temperature from a feed inlet of the double-screw extruder to a die head is 175 ℃,180 ℃,182 ℃,185 ℃,190 ℃ and 180 ℃, the rotating speed of a main machine is 25Hz, the rotating speed of a feeding machine is 4.0Hz, and the PBCT/PBAT alloy material is obtained after water cooling, granulating and drying, wherein: an intrinsic viscosity of 1.27dL/g, a number average molecular weight of 76.7kg/mol, a glass transition temperature of-8.3 ℃, a melting temperature of 128.2 ℃ and a melt index of 5.7g/10min;
(2) And then adding the dried alloy material into a single-screw extrusion film blowing machine, wherein the temperatures of a feeding section, a plasticizing section and a discharging hole template are respectively set at 170 ℃,180 ℃ and 182 ℃, and the rotating speed of a main machine is 20Hz and the feeding rotating speed is 2.0Hz in the blowing process. Film forming by air cooling, drawing and blow molding with a drawing ratio of 40, and the thickness of the final PBCT/PBAT alloy material film is 20-25 μm, and the water vapor permeability coefficient is 3.0X10 -14 g·cm/cm 2 ·s·Pa。
Example 6. Rapid preparation of reactive compatible high Barrier PBCT/PBAT alloy Material and method of processing blow molded articles
(1) 800g of self-made PBCT with 58% aromatic content and 200g of commercial PBAT are fully mixed, and are added into a double-screw extruder, the processing temperature from a feed inlet of the double-screw extruder to a die head is 180 ℃,182 ℃,185 ℃,187 ℃,190 ℃ and 180 ℃, the rotating speed of a main machine is 25Hz, the rotating speed of a feeding machine is 4.0Hz, and the PBCT/PBAT alloy material is obtained after water cooling, granulating and drying, wherein: an intrinsic viscosity of 1.29dL/g, a number average molecular weight of 82.9kg/mol, a glass transition temperature of-7.8 ℃, a melting temperature of 138.9 ℃ and a melt index of 4.9g/10min;
(2) And then adding the dried alloy material into a single-screw extrusion film blowing machine, wherein the temperatures of a feeding section, a plasticizing section and a discharging hole template are respectively set at 180 ℃,190 ℃ and 192 ℃, and the rotating speed of a main machine is 20Hz and the feeding rotating speed is 2.0Hz in the blowing process. Film forming by air cooling, drawing and blow molding with a drawing ratio of 40, and the thickness of the final PBCT/PBAT alloy material film is 20-25 μm, and the water vapor permeability coefficient is 2.4X10 -14 g·cm/cm 2 ·s·Pa。
Comparative example 1 fast preparation of PBST/PBAT alloy Material and processing of blow molded articles
(1) 500g of commercial PBST and 500g of commercial PBAT are fully mixed and added into a double-screw extruder, the processing temperatures from the feed inlet of the double-screw extruder to a die head are 180 ℃,182 ℃,185 ℃,185 ℃,187 ℃,190 ℃ and 180 ℃, the rotating speed of a host machine is 25Hz, the rotating speed of the feed is 4.0Hz, and the PBST/PBAT alloy material is obtained after water cooling, granulating and drying, wherein: intrinsic viscosity 1.17dL/g, number average molecular weight 51.8kg/mol, glass transition temperature-29.7 and-15.3 ℃, melting temperature 119.2 and 129.8 ℃ and melt index 9.4g/10min;
(2) And then adding the dried alloy material into a single-screw extrusion film blowing machine, wherein the temperatures of a feeding section, a plasticizing section and a discharging hole template are respectively set at 180 ℃,190 ℃ and 192 ℃, and the rotating speed of a main machine is 20Hz and the feeding rotating speed is 2.0Hz in the blowing process. Film forming by air cooling, drawing and blow molding with a drawing ratio of 40, and the thickness of the final PBST/PBAT alloy material film is 30-40 μm, and the water vapor permeability coefficient is 19.4X10 -14 g·cm/cm 2 ·s·Pa。
Analysis of results:
1. in comparative example 1, a PBST/PBAT alloy material was prepared and blow-molded in the same procedure as in example 1, and although the PBST/PBAT alloy material could also obtain a degradable film with a high draft ratio, the glass transition temperature and melting temperature of the alloy material were similar to those of PBST and PBAT, no significant mutual approaching occurred, and the water blocking properties were lowered, thus indicating that the blending compatibility of PBST and PBAT was poor and the properties were easily lowered without adding a blending compatibilizer.
While the foregoing description of the embodiments of the present invention has been presented in conjunction with the drawings, it should be understood that it is not intended to limit the scope of the invention, but rather, it is intended to cover all modifications or variations within the scope of the invention as defined by the claims of the present invention.
Claims (10)
1. A reactive compatible high barrier PBCT/PBAT alloy material characterized by having the formula:
wherein m, n, x, y is a natural number and has a value range of 20-300;
m represents the number of repeating units of an aromatic chain segment in PBCT in the main chain of the high-barrier PBCT/PBAT alloy material; n represents the number of repeating units of an aliphatic chain segment of PBCT in the main chain of the high-barrier PBCT/PBAT alloy material; x represents the number of the repeating units of the aliphatic chain segment of the PBAT in the main chain of the high-barrier PBCT/PBAT alloy material, and y represents the number of the repeating units of the aromatic chain segment of the PBAT in the main chain of the high-barrier PBCT/PBAT alloy material.
2. The PBCT/PBAT alloy material of claim 1, wherein the PBCT/PBAT alloy material is prepared from an aromatic-aliphatic copolymer PBCT capped with an ester group and a PBAT capped with a hydroxyl group by melt extrusion blending.
3. The PBCT/PBAT alloy material of claim 2, wherein the PBCT is present in the high barrier PBCT/PBAT alloy material in a weight percentage of 1 to 99%.
4. The PBCT/PBAT alloy material of claim 3, wherein the number of aromatic segments in the PBCT is 1 to 99% of the total number of aliphatic and aromatic segments in the PBCT, in mole percent.
5. The PBCT/PBAT alloy material of claim 4, wherein the PBCT is present in the high barrier PBCT/PBAT alloy material in a ratio of 20 to 80% by weight;
the number of the aromatic chain segments in the PBCT accounts for 40-60% of the total number of the aliphatic chain segments and the aromatic chain segments in the PBCT according to the mole percentage.
6. The PBCT/PBAT alloy material of any of claims 1 to 5, wherein the high barrier PBCT/PBAT alloy material has an intrinsic viscosity of 1.0 to 2.0dL/g, a number average molecular weight of 50 to 100kg/mol, a glass transition temperature of-30 to 44 ℃, a melting temperature of 117 to 230 ℃ and a melt index of 3.0 to 20g/10min.
7. The PBCT/PBAT alloy material of claim 1, wherein the PBCT/PBAT alloy material is prepared by:
(1) Fully mixing PBCT and PBAT according to a certain proportion to obtain a premix;
(2) Extruding and granulating the premix by a double-screw extruder, wherein the temperature of the double-screw extruder is 160-260 ℃ and the rotating speed is 10-30 Hz; the feeding rotating speed is 1.0-5.0 Hz, and the extruded melt is subjected to water cooling, drafting, air drying and granulating to obtain the PBCT/PBAT alloy material;
the mass ratio of the PBCT to the PBAT is 1:99-99:1.
8. The PBCT/PBAT alloy material as claimed in claim 7, wherein,
the number of aromatic chain segments in the PBCT accounts for 1-99% of the total number of aliphatic chain segments and aromatic chain segments in the PBCT.
The number of aromatic segments in the PBAT is 47% of the total number of aliphatic and aromatic segments in the PBAT.
9. A blow molded article of a high barrier PBCT/PBAT alloy material, wherein the blow molded article stock comprises the PBCT/PBAT alloy material of any of claims 1-5, 7-8.
10. The blow molded article of claim 9, wherein the blow molding is performed using a single screw melt extrusion film blowing machine comprising the steps of: feeding the dried alloy material into a feeding section of a single-screw melt extrusion film blowing machine, so that the alloy material is completely melted and plasticized; conveying the melted and plasticized master batch to a discharge port through a screw rod, and performing air cooling, drawing and blow molding to obtain a blow molding product of the PBCT/PBAT alloy material; wherein: the temperature of the template of the feeding section is set between 160 and 260 ℃; the temperature of the plasticizing section template is set between 170 ℃ and 250 ℃; the rotating speed of the host machine is 10-30 Hz; the feeding rotating speed is 1.0-5.0 Hz.
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| CN118108933A (en) * | 2024-04-28 | 2024-05-31 | 康辉新材料科技有限公司 | High-barrier-property poly (terephthalic acid) -succinic acid-carbonic acid-butanediol copolyester and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN118085250A (en) * | 2024-04-28 | 2024-05-28 | 康辉新材料科技有限公司 | Poly (terephthalic acid) -adipic acid-carbonic acid-butanediol ester and preparation method thereof |
| CN118108933A (en) * | 2024-04-28 | 2024-05-31 | 康辉新材料科技有限公司 | High-barrier-property poly (terephthalic acid) -succinic acid-carbonic acid-butanediol copolyester and preparation method thereof |
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