CN117567847A - Production and preparation method of PBAT-PLA composite material directly blended by melt - Google Patents
Production and preparation method of PBAT-PLA composite material directly blended by melt Download PDFInfo
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- 238000000034 method Methods 0.000 claims abstract description 38
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- 239000007788 liquid Substances 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- -1 poly (terephthalic acid) -adipic acid butanediol ester Chemical class 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 8
- 230000004048 modification Effects 0.000 claims description 8
- 238000012986 modification Methods 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
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- 239000002667 nucleating agent Substances 0.000 claims description 6
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- 239000012785 packaging film Substances 0.000 claims description 2
- 229920006280 packaging film Polymers 0.000 claims description 2
- 239000002861 polymer material Substances 0.000 abstract description 3
- 150000002894 organic compounds Chemical class 0.000 abstract description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
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- GOUHYARYYWKXHS-UHFFFAOYSA-N 4-formylbenzoic acid Chemical compound OC(=O)C1=CC=C(C=O)C=C1 GOUHYARYYWKXHS-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
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Abstract
The invention relates to a method for manufacturing a PBAT composite material, in particular to a method for producing and preparing a PBAT-PLA composite material directly blended by melt, belonging to the field of multifunctional composite application of high polymer materials. The invention adopts a continuous polyester preparation process, which comprises a continuous polymerization modified copolyester melt preparation process and a direct melt blending preparation process; in the preparation process of the continuous polymerization modified copolyester melt, refined terephthalic acid (PTA), adipic Acid (AA), 1, 4-Butanediol (BDO) and polylactic acid (PLA) organic compound monomers and polymers are adopted as raw materials, wherein the polylactic acid (PLA) is a high molecular polymer, and the high molecular polymer is crystallized and dried, and is subjected to online melt blending compounding with a PBAT melt from a polyester synthesis device under the conditions of improving the softening point and removing water, and then is subjected to underwater pelleting, so that the PBAT-PLA composite material is prepared.
Description
Technical Field
The invention relates to a method for manufacturing a PBAT composite material, in particular to a method for producing and preparing a PBAT-PLA composite material directly blended by melt, belonging to the field of multifunctional composite application of high polymer materials.
Background
With the increasing demand and production of high molecular polymer products, polymers have become one of the main sources of waste, which has a great influence on the environment. Biodegradable high molecular polymers represent one of the important means for human beings to demonstrate environmental science and solve environmental problems. Among the numerous chemically synthesized biodegradable polymers, PBAT has the characteristics of both poly (adipic acid terephthalate) (PBA) and poly (butylene terephthalate) (PBT), has better ductility and elongation at break, and also has better heat resistance and impact resistance, is one of the best degradable materials for active and market application in the current biodegradable plastic research, and from the practical application trend analysis of performance research and subsequent industrialization, PBAT is the third largest biodegradable plastic gradually formed after starch-based plastic and polylactic acid PLA, and has formed obvious advantages especially in the composite modified biodegradable polymer materials.
However, the high viscosity of PBAT and the low strength after plasticization limit the further development of its processing applications, and in order to overcome these disadvantages, high molecular polymer blending techniques are generally used to improve the processability, mechanical properties and thermal stability of PBAT. Meanwhile, the crystallization capability of PBAT is low, after the synthesis process is finished, amorphous polyester chips are usually prepared by underwater granulating, and then the crystallinity of the amorphous polyester chips is improved by a crystallization drying process, so that the amorphous polyester chips can be blended with other high polymer materials in the screw extrusion process. And a great amount of heat is consumed in the crystallization process, and the circulating hot air is kept to run through the fan, so that a great amount of electric energy is consumed. During crystallization drying, due to friction between polyester chips, a certain amount of chip powder is generated, and the powder enters into a melt for melt compounding, and the functional stability of the composite material is often affected in a form of high melting point and high viscosity. Therefore, how to adopt the direct melt blending technology after the polyester synthesis is finished to solve the problems is also the focus of industry attention.
For example, chinese patent CN111378259a discloses a "method for preparing PBAT-PLA composite material", which implements composite modification by crystallization and drying of two materials and screw extrusion. But the product adopts cooling granulation after PBAT synthesis and recrystallization, drying and melting in the process of PBAT synthesis and compound processing, and has multiple working procedures and increased energy consumption. The PBAT has poor thermal stability compared to conventional polyester products, and the above procedure adds a negative process of thermal degradation of PBAT, which is very detrimental to the processing of the composite material.
Disclosure of Invention
In order to solve the problems, the invention aims to provide a production and preparation method of a PBAT-PLA composite material directly blended by melt. The invention has the advantages of short process flow, less working procedures, reasonable process, stable quality of polyester melt and stable quality of products obtained by post-processing.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a production preparation method of a PBAT-PLA composite material directly blended by melt adopts a continuous polyester preparation and melt conveying process, comprising a synthesis preparation process of a polybutylene terephthalate melt of continuously polymerized copolyester and a composite preparation process of directly conveying the melt and polylactic acid; in the synthesis preparation process of the polybutylene terephthalate-adipate melt, refined terephthalic acid, adipic acid and 1, 4-butanediol organic compound monomers are adopted as raw materials, and calcium carbonate is adopted as a crystallization nucleating agent, so as to prepare a modified copolyester melt; and then the PBAT-PLA composite material is prepared through the procedures of directly conveying the polyester melt, extruding by PLA crystallization drying screw rods, melting on-line compounding, and underwater cooling and granulating of the compound melt.
The production and preparation method of the PBAT-PLA composite material directly blended by the melt comprises the following steps:
(1) Firstly, on continuous polyester equipment, adopting refined terephthalic acid, adipic acid and 1, 4-butanediol organic compound monomers, and firstly continuously and stably metering and adding the refined terephthalic acid, the adipic acid and the 1, 4-butanediol into a slurry preparation tank for pulping according to the proportion of 50-55% of adipic acid in the mol ratio of total dibasic acid to 1:1.1-1:1.3, wherein 100-300ppm of catalyst is added into the slurry preparation tank; then continuously and stably conveying the slurry to a first esterification reaction kettle;
(2) The raw materials complete esterification reaction in a first esterification reaction kettle, the esterification reaction temperature is 200-250 ℃, the esterification reaction pressure is 40-100 kPa/a, and the esterification water enters an environmental protection system for implementation treatment after being separated by a process tower; adding 100-300ppm of titanium catalyst, and allowing the esterified product with the esterification rate (up to 90%) to enter a second esterification reaction kettle for continuous esterification reaction;
(3) Preparing 1-3% suspension by using calcium carbonate and 1, 4-butanediol, storing the suspension in a finished product tank, and stably feeding the suspension into a second esterification reaction kettle through a screw metering pump;
(4) Continuously adding a crystallization nucleating agent accounting for 0.2-0.4 mol percent of total dibasic acid and a 1, 4-butanediol suspension liquid into a second esterification reaction kettle at the same time, controlling the temperature of the second esterification reaction kettle to be 210-250 ℃ and the residence time to be 90-120 minutes, and conveying the uniformly stirred and mixed esterified material to a polycondensation section through pressure difference;
(5) Carrying out polycondensation reaction in a pre-polycondensation reaction kettle, a polycondensation reaction kettle and a final polycondensation reaction kettle at 220-255 ℃ and a vacuum degree of 0.05-15KPa/a to obtain a modified copolyester melt, and conveying the polyester melt into a composite screw extruder through a high-temperature melt gear pump;
(6) Delivering PLA into a crystallization dryer for pre-crystallization and drying according to the proportion of PLA accounting for 15-30% of the mass percentage of the polyester melt, wherein the temperature is 110-130 ℃ so as to improve the softening point of the PLA and remove water; feeding PLA with water content lower than 30 mug/g into a composite screw extruder through a metering device, and adding a compatilizer of PLA and PBAT in the period of 0.05-0.5%;
(7) And fully mixing the PLA and the PBAT polyester melt which are extruded and melted by a screw, further carrying out mixing by a static mixer, sending the compounded PBAT-PLA melt into a granulating system for granulating and forming, drying to ensure that the content of granulating water is less than 0.15%, and packaging and warehousing.
The catalyst in the step (1) is a titanium catalyst.
The crystallization nucleating agent in the step (4) is calcium carbonate.
The compatilizer in the step (6) adopts ADR4370S.
The refined terephthalic acid and adipic acid in the step (1) are powder, and a star feeder, a spiral continuous conveying device and an automatic online continuous weighing device are adopted.
The step (7) comprises the following steps: and conveying the PBAT polyester melt subjected to crystallization modification to a corresponding melt blending production device through a melt conveying gear pump, filtering and pipeline equipment, pre-crystallizing and drying polylactic acid, feeding the polylactic acid into a screw extruder through a metering device for melting, extruding the molten polylactic acid and the PBAT polyester melt subjected to crystallization modification in a screw extruder to form molten polymer fluid, and fully mixing the molten polymer fluid and the PBAT polyester melt.
The filtering and pipeline equipment is pressurized by a melt gear pump, and the temperature of the melt is 230-250 ℃ during melt conveying.
The prepared PBAT-PLA composite material is applied to packaging film materials, and can be applied to terminal products in large supermarkets, farmer markets and express industries, so that the plastic articles with ultra-large consumption can be effectively biologically degraded and controlled after being used, and the effective implementation of environmental protection measures is promoted.
The refined terephthalic acid (PTA) has the appearance of white powder, the molecular weight of 166.131, the purity of more than or equal to 99%, the acid value of 675+/-2 mgKOH/g, the content of p-toluic acid (PT acid) of less than or equal to 150ppm, the 4-hydroxybenzaldehyde (4-CBA) of less than or equal to 25ppm, the hue b value of less than or equal to 1.5, the ash content of less than or equal to 8ppm, the total metal content of less than or equal to 5ppm, the iron content of less than or equal to 1ppm, the chroma number (20% aqueous solution platinum-cobalt) of less than or equal to 10APHA, and the moisture content of less than or equal to 0.2%.
The Adipic Acid (AA) is white crystals or crystalline powder in appearance, has a molecular weight of 146.141, a purity of not less than 99.7%, an acid value of 383+/-2 mgKOH/g, a melting point of not less than 151.5 ℃, a hue b value of not more than 1.5, ash content of not more than 6ppm, nitric acid content of not more than 6ppm, iron content of not more than 0.8ppm, chromaticity number (ammonia solution chromaticity, platinum-cobalt) of not more than 5APHA and moisture of not more than 0.2%.
The 1, 4-Butanediol (BDO) is colorless viscous oily liquid, the molecular weight is 90.12, the purity is more than or equal to 99.5%, the solidifying point is 20.1 ℃, the chromaticity number (20% aqueous solution platinum-cobalt) is less than or equal to 25APHA, the moisture is less than or equal to 0.05%, the acidity (calculated by acetic acid) is less than or equal to 0.002mol/kg, the heavy metal content is less than or equal to 0.1ppm, the ash content is less than or equal to 100ppm, the aldehyde content (calculated by formaldehyde) is less than or equal to 0ppm, and the hydroxyl value is less than or equal to 0.2%.
The polylactic acid (PLA) has a white granular appearance and an intrinsic viscosity IV: 0.2-8 dL/g, melting point 176 ℃, glass transition temperature 60-65 ℃, tensile strength 40-60 MPa, elongation at break 4-10%, elastic modulus 3000-4000 MPa and flexural modulus 100-150 MPa.
The beneficial effects of the invention are as follows:
(1) According to the preparation method, cost and performance factors are integrated, polylactic acid is preferably selected as one of raw materials of the composite material of direct melt blending of PBAT melt, after PBAT synthesis is finished, PLA subjected to crystallization and drying is directly blended and compounded with the PBAT melt, and the addition amount of PLA is 15-30% of that of PBAT, so that the PBAT-PLA blended composite material is prepared;
(2) The modified PBAT copolyester melt is directly sent into a screw extruder through melt conveying equipment (a melt gear pump, a pipeline and a static mixer), PLA is melted after pre-crystallization, drying and screw extrusion, and is directly blended and compounded with the PBAT melt in the screw extruder. The PBAT-PLA composite material directly blended by the melt is produced and prepared, and the melt index of the composite material is 2-10 g/10min due to short flow, less working procedures and reasonable process, the product quality is stable, and the biodegradable film prepared from the composite material has high strength, large elongation and excellent biodegradability, and compared with a PBAT slice crystallization drying and screw extrusion multi-working procedure production device, the production cost is obviously reduced.
Drawings
FIG. 1 is a schematic process flow diagram of the present invention.
Detailed Description
The invention is further described below by means of specific examples.
The implementation is illustrated by the detailed process flow:
(1) Outsourced Purified Terephthalic Acid (PTA) and Adipic Acid (AA) are sent to respective silos for storage.
(2) The PTA slurry preparation tank is continuously added with 1, 4-Butanediol (BDO) and catalyst, and the amounts of the 4-Butanediol (BDO) and the catalyst are automatically controlled according to calculation settings. The PTA is added into a slurry preparation tank by adopting a star feeder, a spiral continuous conveying device and an automatic online continuous weighing device, and the PTA, the 1, 4-Butanediol (BDO) and the catalyst are fully mixed to prepare slurry under the continuous operation and stirring of a stirrer. The slurry is continuously fed into the first esterification reaction kettle from the bottom of the blending tank through a slurry conveying pump and a slurry flowmeter.
The AA slurry preparation tank is continuously added with 1, 4-Butanediol (BDO) and catalyst, and the amounts of the 4-Butanediol (BDO) and the catalyst are automatically controlled according to calculation settings. AA is added into a slurry preparation tank by adopting a star feeder, a spiral continuous conveying device and an automatic online continuous weighing device, and AA, 1, 4-Butanediol (BDO) and a catalyst are fully mixed to prepare slurry under the continuous operation and stirring of a stirrer. The slurry is continuously fed into the first esterification reaction kettle from the bottom of the blending tank through a slurry conveying pump and a slurry flowmeter.
(3) The esterification reaction system is provided with two esterification reaction kettles in total. The esterification reaction of PTA, AA and BDO is carried out in the first esterification reaction kettle, the esterification rate of the reaction can be controlled to be more than 98% by adjusting the temperature, the pressure and the liquid level of the reactor, and the catalyst is continuously added into the first esterification reaction kettle. The esterified substances reaching the esterification rate enter a second esterification reaction kettle from a first esterification reaction kettle through a discharge pump, and the esterification rate can be improved to more than 99% by controlling certain reaction temperature, pressure and liquid level in the second esterification reactor. The vapor phase of the two esterification reaction kettles enters the same process tower for separating BDO, esterification reaction water and THF, the separated heavy component BDO flows back to the first esterification reaction kettle and the second esterification reaction kettle through a conveying pump, the redundant component BDO enters a raw material preparation system, after being condensed by a heat exchanger, part of condensate flows back to the process tower, the rest of condensate is taken as production wastewater to enter a Tetrahydrofuran (THF) purification device for recovering tetrahydrofuran, the recovered tetrahydrofuran enters a special storage tank for THF, the wastewater of the purification device enters a sewage treatment station for biochemical treatment, and COD reaches the standard and is discharged to a sewage treatment plant of an industrial area for further treatment.
(4) A pre-polycondensation reaction kettle and a polycondensation reaction kettle are arranged, wherein the pre-polycondensation reaction kettle is a vertical reaction kettle, the polycondensation reaction kettle is a horizontal reaction kettle, and a horizontal stirrer is arranged. Under the action of the second-stage pressure difference, the esterified substance firstly enters the pre-polycondensation reaction kettle through an outlet pipeline of the second esterification kettle, and then enters the polycondensation reaction kettle through a discharge pump and a regulating valve. The pre-polycondensation reaction kettle and the polycondensation reaction kettle share a set of vacuum injection system for condensation polymerization reaction, and the vacuum injection system consists of a BDO steam generator, a steam injection series pump, a BDO circulating spray subsystem, a vacuum pump system and a tail gas system. A scraper condenser is arranged between the pre-polycondensation reaction kettle and the vacuum injection system, gas phase matters generated by the reaction enter the scraper condenser to reversely contact with the sprayed BDO, the entrainment matters in the gas phase are trapped, the BDO mainly comprise BDO, water, oligomers and the like, BDO condensate is collected in a liquid seal tank and conveyed by a pump, cooled by a plate heat exchanger and recycled, and the redundant matters are conveyed into a process tower to be separated and recycled. The scraper condenser which is the same as the pre-polycondensation reaction kettle and auxiliary equipment thereof are also arranged between the polycondensation reaction kettle and the vacuum injection system. And (3) conveying the polymer reaching the set polymerization degree into a final polymerization reaction kettle by adopting a high-temperature gear pump, and further carrying out condensation polymerization.
(5) Setting two final polycondensation reaction kettles, controlling the operation pressure in a high vacuum state, and controlling the vacuum degree to enable the viscosity of the melt to reach the index requirement, so as to prepare the PBAT polyester melt. In order to control the vacuum degree of the final polycondensation system, chilled water is used as a cooling medium for the BDO spraying liquid. Fresh BDO is added into a scraper condenser and a BDO steam generator of the final polycondensation reaction kettle, BDO condensate is also collected in the liquid seal tank, and the BDO condensate can be directly used for preparing slurry due to lower water content. A BDO steam generator and a steam jet pump are arranged to generate vacuum, a mechanical vacuum pump is used as non-condensable gas discharging power of the system, and the vacuum degree of condensation polymerization reaction is controlled by adjusting the BDO steam amount fed into an inlet of the jet pump.
(6) The polyester melt is discharged and pressurized by adopting a screw discharging machine and a high-temperature gear pump, filtered impurities by the melt, sent to a screw extruder by a melt distribution system, melted and compounded with PLA, and the redundant part of the PBAT polyester melt is pelletized by a pelletizer, and pelletized into a spherical shape. A packing machine is arranged to pack the slices of the composite grain, and then the slices are sent to a finished product warehouse for storage by a forklift. Two 2300 kilocalories per hour of natural gas heat conduction oil boilers are arranged to provide heat required by chemical reaction and system heat preservation for the polyester device.
(7) And (3) feeding the PLA into a crystallization dryer to perform pre-crystallization and drying according to the preset mass percentage of the PLA in the PBAT polyester melt and the crystallization drying temperature so as to improve the softening point of the PLA and remove water. PLA with water content lower than a specified value is fed into a compound screw extruder to be melted and compounded with PBAT polyester melt from a polyester device, and the compatilizer ADR4370S of PLA and PBAT is added according to a preset adding amount during the melting and compounding process. And (5) granulating the compounded melt by a slicing production system, wherein the granulated melt is in a spherical shape.
Example 1
A production preparation method of a PBAT-PLA composite material directly blended by melt adopts a continuous polyester preparation process, comprising a continuous polymerization modified copolyester melt preparation process and a direct melt blending preparation process; in the preparation process of the continuous polymerization modified copolyester melt, refined terephthalic acid (PTA), adipic Acid (AA), 1, 4-Butanediol (BDO) and polylactic acid (PLA) organic compound monomers and polymers are adopted as raw materials, wherein the polylactic acid (PLA) is a high molecular polymer, and the high molecular polymer is crystallized and dried, and is subjected to online melt blending compounding with a PBAT melt from a polyester synthesis device under the condition of improving the softening point and the danger-free water content, and then subjected to underwater pelleting, so that the PBAT-PLA composite material is prepared.
The preparation process of the continuous polymerization modified copolyester melt comprises the following steps:
(1) Firstly, on continuous polyester equipment, adopting refined terephthalic acid, adipic acid and 1, 4-butanediol organic compound monomers, and firstly continuously and stably metering and adding refined terephthalic acid, adipic acid and 1, 4-butanediol into a slurry preparation tank for pulping according to the mole percentage of adipic acid to total diacid of 50% -55% and the mole ratio of total diacid to dihydric alcohol of 1:1.1-1:1.3, and adding 100-200ppm of titanium catalyst into the slurry preparation tank; then continuously and stably conveying the slurry to a first esterification reaction kettle; the refined terephthalic acid and adipic acid in the step (1) are powder, and a star feeder, a spiral continuous conveying device and an automatic online continuous weighing device are adopted.
(2) The raw materials complete esterification reaction in a first esterification reaction kettle, the esterification reaction temperature is 200-250 ℃, the esterification reaction pressure is 40-100 kPa/a, and the esterification water enters an environmental protection system for implementation treatment after being separated by a process tower; adding 100-300ppm of titanium catalyst into the first esterification reaction kettle, and allowing the esterified substance with the specified esterification rate to enter the second esterification reaction kettle for continuous esterification reaction;
(3) Preparing 1-3% suspension by using calcium carbonate and 1, 4-butanediol, storing the suspension in a finished product tank, and stably feeding the suspension into a second esterification reaction kettle through a screw metering pump;
(4) Continuously adding calcium carbonate and 1, 4-butanediol suspension accounting for 0.2-0.4 mol percent of total dibasic acid into the second esterification reaction kettle at the same time, controlling the temperature of the second esterification reaction kettle to be 210-250 ℃ and the residence time to be 90-120 minutes, and conveying the uniformly stirred and mixed esterified matter to a polycondensation working section through pressure difference;
(5) And (3) carrying out polycondensation reaction in a pre-polycondensation reaction kettle, a polycondensation reaction kettle and a final polycondensation reaction kettle at the temperature of 220-255 ℃ and the vacuum degree of 0.05-15KPa/a to obtain the modified copolyester melt. The polyester melt is fed into the compound screw extruder by a high temperature melt gear pump.
(6) According to the proportion of PLA accounting for 15-30% of the mass percentage of the polyester melt, the PLA is sent into a crystallization dryer for pre-crystallization and drying at 110-130 ℃ so as to improve the softening point of the PLA and remove water. Feeding PLA with water content lower than 30 mug/g into a composite screw extruder through a metering device, and adding a compatilizer ADR4370S of PLA and PBAT in the period of 0.05-0.5%;
(7) And fully mixing the PLA and the PBAT polyester melt which are extruded and melted by a screw, further carrying out mixing by a static mixer, sending the compounded PBAT-PLA melt into a granulating system for granulating and forming, drying to ensure that the content of granulating water is less than 0.15%, and packaging and warehousing.
The PBAT-PLA direct blending preparation process comprises the following steps: and conveying the PBAT polyester melt subjected to crystallization modification to a corresponding melt blending production device through a melt conveying gear pump, filtering and pipeline equipment, pre-crystallizing polylactic acid, feeding the polylactic acid into a screw extruder through a metering device, melting, extruding the polylactic acid and the PBAT polyester melt subjected to crystallization modification in a screw extruder to form molten polymer fluid, and carrying out melt blending with the PBAT polyester melt. The melt conveying pipeline device is pressurized by a melt gear pump, and the temperature of the melt during melt conveying is 230-250 ℃.
The refined terephthalic acid (PTA) has the appearance of white powder, the molecular weight of 166.131, the purity of more than or equal to 99%, the acid value of 675+/-2 mgKOH/g, the content of p-toluic acid (PT acid) of less than or equal to 150ppm, the 4-hydroxybenzaldehyde (4-CBA) of less than or equal to 25ppm, the hue b value of less than or equal to 1.5, the ash content of less than or equal to 8ppm, the total metal content of less than or equal to 5ppm, the iron content of less than or equal to 1ppm, the chroma number (20% aqueous solution platinum-cobalt) of less than or equal to 10APHA, and the moisture content of less than or equal to 0.2%.
The Adipic Acid (AA) is white crystals or crystalline powder in appearance, has a molecular weight of 146.141, a purity of not less than 99.7%, an acid value of 383+/-2 mgKOH/g, a melting point of not less than 151.5 ℃, a hue b value of not more than 1.5, ash content of not more than 6ppm, nitric acid content of not more than 6ppm, iron content of not more than 0.8ppm, chromaticity number (ammonia solution chromaticity, platinum-cobalt) of not more than 5APHA and moisture of not more than 0.2%.
The 1, 4-Butanediol (BDO) is colorless viscous oily liquid, the molecular weight is 90.12, the purity is more than or equal to 99.5%, the solidifying point is 20.1 ℃, the chromaticity number (20% aqueous solution platinum-cobalt) is less than or equal to 25APHA, the moisture is less than or equal to 0.05%, the acidity (calculated by acetic acid) is less than or equal to 0.002mol/kg, the heavy metal content is less than or equal to 0.1ppm, the ash content is less than or equal to 100ppm, the aldehyde content (calculated by formaldehyde) is less than or equal to 0ppm, and the hydroxyl value is less than or equal to 0.2%.
The polylactic acid (PLA) has a white granular appearance and an intrinsic viscosity IV: 0.2-8 dL/g, melting point 176 ℃, glass transition temperature 60-65 ℃, tensile strength 40-60 MPa, elongation at break 4-10%, elastic modulus 3000-4000 MPa and flexural modulus 100-150 MPa.
(8) Performance detection
The performance parameters of the PBAT/PLA composite material prepared by this method are shown in Table 1. The prepared PBAT/PLA is a novel film-grade full-biodegradable material, has good flexibility and film forming property, and can replace traditional film blowing materials such as PP, PE and the like.
TABLE 1 Performance parameters of PBAT/PLA composite materials
| Project | Rated value | Test conditions |
| Specific gravity (g/cm 3) | 1.27 | / |
| Melt flow Rate (g/10 min) | 15.2 | 210℃/2.16kg |
| Heat distortion temperature (DEG C) | 64.8 | 0.45MPa |
| Melting point (. Degree. C.) | 139.2 | / |
| Tensile Strength (MPa) | 7.2 | 50mm/min |
| Elongation at break (%) | ≥199 | 50mm/min |
| Shore hardness (A) | 94 | / |
The above embodiments are only for illustrating the inventive concept of the present invention and not for limiting the protection of the claims of the present invention, and all the insubstantial modifications of the present invention using the concept shall fall within the protection scope of the present invention.
Claims (9)
1. A production and preparation method of a PBAT-PLA composite material directly blended by melt adopts a continuous polyester preparation and melt conveying process, and is characterized in that: comprises a synthesis preparation process of a poly (terephthalic acid) -adipic acid butanediol ester melt of continuous polymerization copolyester and a composite preparation process of direct melt conveying and polylactic acid; in the synthesis preparation process of the polybutylene terephthalate-adipate melt, refined terephthalic acid, adipic acid and 1, 4-butanediol organic compound monomers are adopted as raw materials, and calcium carbonate is adopted as a crystallization nucleating agent, so as to prepare a modified copolyester melt; and then the PBAT-PLA composite material is prepared through the procedures of directly conveying the polyester melt, extruding by PLA crystallization drying screw rods, melting on-line compounding and granulating the compound melt.
2. The method of producing and preparing a melt-directly blended PBAT-PLA composite material of claim 1, comprising the steps of:
(1) Firstly, on continuous polyester equipment, adopting refined terephthalic acid, adipic acid and 1, 4-butanediol organic compound monomers, and firstly continuously and stably metering and adding the refined terephthalic acid, the adipic acid and the 1, 4-butanediol into a slurry preparation tank for pulping according to the proportion of 50-55% of adipic acid in the mol ratio of total dibasic acid to 1:1.1-1:1.3, wherein 100-300ppm of catalyst is added into the slurry preparation tank; then continuously and stably conveying the slurry to a first esterification reaction kettle;
(2) The raw materials complete esterification reaction in a first esterification reaction kettle, the esterification reaction temperature is 200-250 ℃, the esterification reaction pressure is 40-100 kPa/a, and the esterification water enters an environmental protection system for implementation treatment after being separated by a process tower; adding 100-300ppm of titanium catalyst, and allowing the esterified substance with the esterification rate to enter a second esterification reaction kettle for continuous esterification reaction;
(3) Preparing 1-3% suspension by using calcium carbonate and 1, 4-butanediol, storing the suspension in a finished product tank, and stably feeding the suspension into a second esterification reaction kettle through a screw metering pump;
(4) Continuously adding a crystallization nucleating agent accounting for 0.2-0.4 mol percent of total dibasic acid and a 1, 4-butanediol suspension liquid into a second esterification reaction kettle at the same time, controlling the temperature of the second esterification reaction kettle to be 210-250 ℃ and the residence time to be 90-120 minutes, and conveying the uniformly stirred and mixed esterified material to a polycondensation section through pressure difference;
(5) Carrying out polycondensation reaction in a pre-polycondensation reaction kettle, a polycondensation reaction kettle and a final polycondensation reaction kettle at 220-255 ℃ and a vacuum degree of 0.05-15KPa/a to obtain a modified copolyester melt, and conveying the polyester melt into a composite screw extruder through a high-temperature melt gear pump;
(6) Delivering PLA into a crystallization dryer for pre-crystallization and drying according to the proportion of PLA accounting for 15-30% of the mass percentage of the polyester melt, wherein the temperature is 110-130 ℃ so as to improve the softening point of the PLA and remove water; feeding PLA with water content lower than 30 mug/g into a composite screw extruder through a metering device, and adding a compatilizer of PLA and PBAT in the period of 0.05-0.5%;
(7) And fully mixing the PLA and the PBAT polyester melt which are extruded and melted by a screw, further carrying out mixing by a static mixer, sending the compounded PBAT-PLA melt into a granulating system for granulating and forming, drying to ensure that the content of granulating water is less than 0.15%, and packaging and warehousing.
3. The method for producing and preparing the melt-directly blended PBAT-PLA composite material according to claim 2, wherein the method comprises the following steps: the catalyst in the step (1) is a titanium catalyst.
4. The method for producing and preparing the melt-directly blended PBAT-PLA composite material according to claim 2, wherein the method comprises the following steps: the crystallization nucleating agent in the step (4) is calcium carbonate.
5. The method for producing and preparing the melt-directly blended PBAT-PLA composite material according to claim 2, wherein the method comprises the following steps: the compatilizer in the step (6) adopts ADR4370S.
6. The method for producing and preparing the melt-directly blended PBAT-PLA composite material according to claim 2, wherein the method comprises the following steps: the refined terephthalic acid and adipic acid in the step (1) are powder, and a star feeder, a spiral continuous conveying device and an automatic online continuous weighing device are adopted.
7. The method of producing and preparing a melt-directly blended PBAT-PLA composite material of claim 1, wherein the step (7) includes the steps of: and conveying the PBAT polyester melt subjected to crystallization modification to a corresponding melt blending production device through a melt conveying gear pump, filtering and pipeline equipment, pre-crystallizing and drying polylactic acid, feeding the polylactic acid into a screw extruder through a metering device for melting, extruding the molten polylactic acid and the PBAT polyester melt subjected to crystallization modification in a screw extruder to form molten polymer fluid, and fully mixing the molten polymer fluid and the PBAT polyester melt.
8. The method for producing and preparing the directly melt-blended PBAT-PLA composite material according to claim 7, wherein the method comprises the following steps: the filtering and pipeline equipment is pressurized by a melt gear pump, and the temperature of the melt is 230-250 ℃ during melt conveying.
9. The PBAT-PLA composite material prepared by the production and preparation method of the melt direct blending PBAT-PLA composite material in claim 1 is applied to packaging film materials.
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