CN111100427A - Aliphatic aromatic copolyester blend with improved crystallization performance and preparation method and application thereof - Google Patents
Aliphatic aromatic copolyester blend with improved crystallization performance and preparation method and application thereof Download PDFInfo
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- CN111100427A CN111100427A CN201811251296.9A CN201811251296A CN111100427A CN 111100427 A CN111100427 A CN 111100427A CN 201811251296 A CN201811251296 A CN 201811251296A CN 111100427 A CN111100427 A CN 111100427A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/20—Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The invention relates to an aliphatic aromatic copolyester blend with improved crystallinity, a preparation method and application thereof, and mainly solves the technical problems of low crystallization temperature and low crystallization speed of biodegradable aliphatic aromatic copolyester in the prior art. The aliphatic aromatic copolyester blend comprises the following components in parts by mass: (1) 90-99 parts of biodegradable aliphatic aromatic copolyester; (2) 1-10 parts of aliphatic aromatic polyester with low aliphatic diacid content; the technical scheme that the biodegradable aliphatic aromatic copolyester and the aliphatic aromatic copolyester with low aliphatic diacid content have the same repeating unit better solves the problem and can be applied to the production of high-crystallinity biodegradable aliphatic aromatic copolyester materials.
Description
Technical Field
The invention discloses an aliphatic aromatic copolyester blend with improved crystallinity as well as a preparation method and application thereof.
Technical Field
The aliphatic aromatic copolyester is a fast-developing high molecular material, is usually obtained by random copolymerization of aliphatic diacid, aromatic diacid and aliphatic diol, and can combine the advantageous properties of the aliphatic polyester and the aromatic polyester to obtain a practical material with good strength and toughness. The aromatic polyester segments serve primarily as a dilution cost in addition to providing performance support; the aliphatic polyester segment is generally biodegradable on the basis of providing performance support. The aliphatic aromatic copolyester as a whole will have biodegradability after the aliphatic segment content reaches a certain level, and it is reported in the literature that the biodegradability of the material as a whole is substantially lost after the mole fraction of aliphatic diacid to total diacid is reduced to 38% (n.honda, i.taniguchi, m.miyamoto, y.kimura, Macromolecular Bioscience,2003,3, 189-. On the other hand, the cost is one of the important factors restricting the large-scale application of the biodegradable polymer material, so in order to reduce the cost of the biodegradable aliphatic aromatic copolyester material, the dosage of the low-price aromatic diacid should be as large as possible on the basis of ensuring the biodegradability. Combining the two factors, the molar fraction of the aliphatic diacid in the biodegradable copolyester product for industrial production accounts for 45-60% of the total diacid.
Both aliphatic and aromatic polyesters have inherently higher crystallization temperatures (typically peak crystallization temperatures above 100 ℃) and faster crystallization rates. However, when the aliphatic and aromatic chain segments are randomly copolymerized, the crystallization performance of the material is remarkably reduced, and particularly in the biodegradable aliphatic and aromatic copolyester material, when the mole fraction of the aliphatic polyester chain segments in the total chain segments is about 50%, the crystallization peak temperature of the material is reduced to below 50 ℃, and the subsequent processing application of the material is seriously influenced.
At present, the most common method for improving the crystallization performance of the high polymer material is to add an inorganic crystallization nucleating agent [ Zhupenfei, a nucleating agent of polybutylene succinate-co-terephthalate (PBST) and copolymerization modification research, Master academic thesis of Donghua university, 2013], which can actually improve the crystallization performance of the material to a certain extent, but the addition of the inorganic nucleating agent may affect the polymerization preparation process of the material and increase the cost, and the nucleating effect of the inorganic nucleating agent is uneven due to problems of lattice matching and the like. Theoretically, the nuclei of the polymer itself are the best nucleating agent due to a perfect match in lattice parameters. The literature reports that when S (succinic acid) in PBST accounts for less than 70% of the total diacid content, PBST shows a PBT crystal form when crystallized, and when S (succinic acid) accounts for more than 70% of the total diacid content, PBST shows a PBS crystal form when crystallized, and when S (succinic acid) accounts for 70%, the PBS crystal form and the PBT crystal form are both good; and the crystallization performance of the PBST shows a trend of weakening firstly and then enhancing with the increase of the content of the succinic acid, wherein the turning point is 50-60 mol%. [ Guo Bao-Hua, Ding Hui-Ge, Xu Xiao-Lin, Xu Jun, Sun Yuan-Bi, Chemical Journal of Chinese University,2003,24(12), 2312-.
The aliphatic diacid content of the biodegradable PBAT and PBST researched by the invention is 50-59%, and the PBT crystal form is mainly used, so that the similar aliphatic aromatic copolyester with the PBT crystal form and better crystallization performance and low aliphatic diacid content is selected as a crystal nucleus to promote the integral crystallization of the material. Due to the poor biodegradability of aliphatic aromatic copolyesters with a low aliphatic diacid content, there have been few reports of adding them to biodegradable aliphatic aromatic copolyesters. The invention well promotes the crystallization performance by adding a small amount of similar aliphatic aromatic copolyester with low aliphatic diacid content (not more than 5 percent, even not more than 3 percent under certain conditions) into PBAT and PBST, meets the requirement of continuous grain cutting, has little influence on the biodegradability of the copolyester, and obtains good technical effect.
Disclosure of Invention
One of the technical problems to be solved by the invention is the problems of low crystallization temperature and low crystallization speed of biodegradable aliphatic aromatic copolyester in the prior art, and the invention provides the aliphatic aromatic copolyester blend with improved crystallization performance, and the blend has the advantage of rapid crystallization in a room-temperature water bath.
The second technical problem to be solved by the invention is to provide a preparation method of the aliphatic aromatic copolyester blend with improved crystallinity corresponding to the first technical problem, the blend obtained by the blending method improves the crystallization property of the biodegradable aliphatic aromatic copolyester, is simple and easy to implement, can effectively improve the crystallization property of the biodegradable aliphatic aromatic copolyester, improves the processability and expands the application field.
The invention provides an application method of aliphatic aromatic copolyester mixture with improved crystallinity corresponding to one of the technical problems.
In order to solve one of the above technical problems, the technical scheme adopted by the invention is as follows: an aliphatic aromatic copolyester blend comprises the following components in parts by mass:
(1) 90-99 parts of biodegradable aliphatic aromatic copolyester;
(2) 1-10 parts of aliphatic aromatic polyester with low aliphatic diacid content;
wherein the biodegradable aliphatic aromatic copolyester and the aliphatic aromatic polyester with low aliphatic diacid content contain the same repeating units.
In the technical scheme, the time for the aliphatic aromatic copolyester melt to reach 30HD hardness after being cooled in a water bath at normal temperature (20-35 ℃) is at least 50% shorter than the time for the biodegradable aliphatic aromatic copolyester raw material melt to reach 30HD hardness in the same state, and further preferably can be 100% shorter.
In the technical scheme, the hardness testing method is an online testing method, namely, timing is started when the melt enters the normal-temperature water bath, and the hardness of the sample strip is rapidly detected in the water bath in real time by using a D-type handheld Shore durometer, so that the relation between the time when the melt enters the water bath and the hardness is obtained.
In the technical scheme, the biodegradable aliphatic aromatic copolyester comprises an aliphatic diacid or aliphatic diacid derivative chain segment, an aromatic diacid or aromatic diacid derivative chain segment and at least one aliphatic diol chain segment; the mole fraction of the aliphatic diacid in the total diacid is 50 to 59 percent, and the mole fraction of the aliphatic diacid in the total diacid is more preferably 50 to 57 percent.
In the above technical solution, the biodegradable aliphatic aromatic copolyester is preferably at least one of polybutylene succinate-co-terephthalate and polybutylene adipate-co-terephthalate.
In the above technical solution, the aliphatic aromatic copolyester with low aliphatic diacid content comprises an aliphatic diacid or aliphatic diacid derivative segment, an aromatic diacid or aromatic diacid derivative segment, and at least one aliphatic diol segment; wherein the molar fraction of the aliphatic diacid in the total diacid is 10-40 percent and is lower than the content of the aliphatic diacid in the biodegradable aliphatic aromatic copolyester.
In the technical scheme, the aliphatic aromatic copolyester with low aliphatic diacid content is selected from at least one of polybutylene succinate-co-terephthalate and polybutylene adipate-co-terephthalate.
In the technical scheme, the aliphatic aromatic copolyester blend further comprises 0-5 parts of functional additives, and the functional additives comprise at least one of a chain extender, a compatilizer and a plasticizer.
In order to solve the second technical problem, the invention adopts the technical scheme that: a method for preparing an aliphatic aromatic copolyester blend according to any one of the technical solutions to solve one of the above technical problems, comprising the steps of:
and (2) preparing the biodegradable aliphatic aromatic copolyester, the aliphatic aromatic polyester with low aliphatic diacid content and optional functional auxiliary agent by a blending method according to the mass parts to obtain the aliphatic aromatic copolyester blend.
In the above technical solution, the blending method is at least one of a solution blending method and a melt blending method, and more preferably a melt blending method, and preferably a twin-screw extruder is used for melt blending.
In the technical scheme, the solution method is to dissolve appropriate amounts of biodegradable aliphatic aromatic copolyester, aliphatic aromatic polyester with low aliphatic diacid content and other functional auxiliaries into an appropriate solvent, fully stir and mix the mixture uniformly, and remove the solvent to obtain the biodegradable aliphatic aromatic copolyester blend with high crystallinity.
In the technical scheme, the melting method comprises the steps of melting the biodegradable aliphatic aromatic copolyester, the aliphatic aromatic polyester with low aliphatic diacid content and other functional auxiliaries in proportion, stirring and mixing, and cooling to obtain the biodegradable aliphatic aromatic copolyester blend with high crystallinity.
In the above technical solution, the melting method is preferably at least one of an internal mixing method and a twin-screw extrusion method, and more preferably a twin-screw extrusion method.
In the technical scheme, the processing temperature of the melting method is preferably 150-300 ℃, and more preferably 180-260 ℃.
In order to solve the third technical problem, the invention adopts the technical scheme that: an application method of the aliphatic aromatic copolyester blend in the technical scheme for solving one of the technical problems.
In the above technical solutions, the application method is not particularly limited, and those skilled in the art can utilize the method according to the prior art, for example, but not limited to, cooling granulation for improving the synthesis of biodegradable aliphatic aromatic copolyester, and application in the fields of film making, injection molding, spinning, and the like.
In the above technical solution to solve the technical problem, the preferable solution is as follows:
1. biodegradable aliphatic aromatic copolyester
The aliphatic aromatic copolyester is obtained by condensation copolymerization of at least one α, omega-aliphatic diacid or α, omega-aliphatic diacid anhydride or α, omega-aliphatic diacid halide and at least one aromatic diacid or aromatic diacid anhydride or aromatic diacid halide with at least one aliphatic diol, in order to improve the molecular weight of a final product, a branching agent such as polyol, polyacid anhydride or polyacid halide with polyfunctionality (the functionality is more than 2) accounting for 0.1 to 3 percent of the total mass fraction can be added into a polymerization system, in order to meet the biodegradability of the whole aliphatic aromatic copolyester material, wherein the mole ratio of α, omega-aliphatic diacid or derivatives thereof accounting for the total diacid is higher than 38 percent.
Representative aliphatic diacids suitable for use in the present invention include substituted and unsubstituted organic diacids including straight chain alkyl, branched chain alkyl, cyclic alkyl, and alkyl groups with unsaturation, among others, aliphatic diacids include α, omega-aliphatic diacids having from 2 to 22 backbone carbon atoms, including oxalic acid, 1, 3-malonic acid, succinic acid (1, 4-succinic acid), glutamic acid (1, 5-glutaric acid), adipic acid (1, 6-adipic acid), 1, 7-pimelic acid, 1, 8-suberic acid, 1, 9-azelaic acid, 1, 10-sebacic acid up to 22 carbon atoms and diacids with other substituents such as cyclohexyl.
The aromatic diacid suitable for the present invention is preferably at least one diacid selected from terephthalic acid, 1, 4-naphthalenedicarboxylic acid, 2, 7-naphthalenedicarboxylic acid, 2, 6-naphthalenedicarboxylic acid, 2, 7-naphthalenedicarboxylic acid, 4, 4 '-diphenyletherdicarboxylic acid, 4, 3' -diphenyletherdicarboxylic acid, 4, 4 '-diphenylthioether-dicarboxylic acid, 4, 3' -diphenylthioether-dicarboxylic acid, 4, 4 '-diphenylsulfone-dicarboxylic acid, 4, 3' -diphenylsulfone-dicarboxylic acid, 4, 4 '-benzophenonedicarboxylic acid, 4, 3' -benzophenonedicarboxylic acid, and the like; or the derivative of the aromatic diacid is preferably at least one selected from the acid anhydrides, esters, acid halides and the like prepared from the above diacids.
Aliphatic diols suitable for preparing biodegradable aliphatic polyesters in the present invention include ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 1, 2-butanediol, 1, 3-butanediol, 1, 4-butanediol, 1, 2-pentanediol, 1, 3-pentanediol, 1, 4-pentanediol, 1, 5-pentanediol, 1, 2-hexanediol, 1, 3-hexanediol, 1, 4-hexanediol, 1, 5-hexanediol, 1, 6-hexanediol, 1, 2-heptanediol, 1, 3-heptanediol, 1, 4-heptanediol, 1, 5-heptanediol, 1, 6-heptanediol, 1, 7-heptanediol, 1, 2-octanediol, 1, 3-octanediol, 1, 4-octanediol, 1, 5-octanediol, 1, 6-octanediol, 1, 7-octanediol, 1, 8-octanediol, 1, 2-nonanediol, 1, 3-nonanediol, 1, 4-nonanediol, 1, 5-nonanediol, 1, 6-nonanediol, 1, 7-nonanediol, 1, 8-nonanediol, 1, 9-nonanediol, 1, 2-decanediol, 1, 3-decanediol, 1, 4-decanediol, 1, 5-decanediol, 1, 6-decanediol, 1, 7-decanediol, 1, 8-decanediol, 1, 9-decanediol, 1, 10-decanediol up to a diol having a carbon number of 24 and diols having other substituents such as cyclohexyl.
Biodegradable aliphatic aromatic copolyesters suitable for use in the invention include chain-extended aliphatic aromatic polyesters, and a variety of compounds or polymers reactive with carboxyl or hydroxyl groups can be used as chain extenders, including, for example, isocyanates containing two or more functional groups such as hexamethylene diisocyanate (HMDI). Suitable chain extenders include compounds containing multiple epoxy functional groups, such as those produced by BASF
ADR-4368C,
ADR-4368CS，
ADR-4370, and the like.
The biodegradable aliphatic aromatic copolyester suitable for the present invention is preferably polyethylene terephthalate-co-oxalate, polyethylene terephthalate-co-malonate, polyethylene terephthalate-co-succinate, polyethylene terephthalate-co-glutarate, polyethylene terephthalate-co-adipate, polyethylene terephthalate-co-suberate, polypropylene terephthalate-co-oxalate, polypropylene terephthalate-co-malonate, polypropylene terephthalate-co-succinate, polypropylene terephthalate-co-glutarate, polypropylene terephthalate-co-adipate, polypropylene terephthalate-co-suberate, polypropylene terephthalate-co-adipate, polyethylene terephthalate-co-suberate, polyethylene terephthalate-co-adipate, polyethylene terephthalate-co-succinate, polyethylene, Polytrimethylene terephthalate-co-sebacate, polybutylene terephthalate-co-oxalate, polybutylene terephthalate-co-malonate, polybutylene succinate-co-terephthalate, polybutylene terephthalate-co-glutarate, polybutylene terephthalate-co-adipate, polybutylene terephthalate-co-suberate, polyhexamethylene terephthalate-co-oxalate, polyhexamethylene terephthalate-co-malonate, at least one of poly (ethylene terephthalate-co-succinate), poly (ethylene terephthalate-co-glutarate), poly (ethylene terephthalate-co-adipate), poly (ethylene terephthalate-co-suberate), and the like.
The biodegradable aliphatic aromatic copolyester particularly suitable for the present invention is at least one of polybutylene terephthalate-co-adipate (PBAT) and polybutylene succinate-co-terephthalate (PBST). Generally, in order to ensure complete biodegradability, the mole fraction of aliphatic polyester chain segments in the above aliphatic aromatic copolyester in the total chain segments is about 50%, which makes the overall crystallization temperature of the biodegradable aliphatic aromatic copolyester material lower and the crystallization rate slower.
The biodegradable aliphatic aromatic copolyesters suitable for use in the present invention need to satisfy, in addition to the preferred above-mentioned categories: the biodegradable aliphatic aromatic copolyester is biodegradable aliphatic aromatic copolyester melt or particles directly prepared from a polymerization device, and the biodegradable aliphatic aromatic copolyester melt or particles can be biodegradable aliphatic aromatic copolyester melt or particles added with functional additives such as a crystallization nucleating agent and the like in a synthesis stage.
2. High molecular melt blending method
The biodegradable aliphatic aromatic copolyester melt blending device suitable for the present invention is preferably, but not limited to: internal mixers, Farrel continuous mixers, Banbury mixers, single screw extruders, multiple screw extruders (more than two screws), reciprocating single screw extruders such as Buss reciprocating single screw extruders (Buss Ko-Kneader), thin tube melt extrusion processing equipment, and the like. The above process can also be combined with the steps of addition of an auxiliary agent, melt chain extension, processing and forming and the like.
The improvement of the crystallization performance of the high polymer is mainly reflected in the improvement of parameters such as crystallization temperature, crystallization rate, crystallinity and the like, and the defects of the crystallization performance of the biodegradable aliphatic aromatic copolyester are mainly represented by that the crystallization temperature is too low, the crystallization speed is too slow, and the hardening speed is slow, so that the continuous processing is difficult. According to the invention, by adding the same aliphatic aromatic copolyester with low aliphatic diacid content and other functional auxiliaries in proper amount, the crystallinity of the biodegradable aliphatic aromatic copolyester is effectively improved, and a better technical effect is obtained.
By adopting the technical scheme of the invention, the obtained aliphatic aromatic copolyester blend with improved crystallinity has high crystallization rate, and the time for the melt of the aliphatic aromatic copolyester blend to reach 30HD hardness through water bath cooling at normal temperature (20-35 ℃) is at least 50% shorter than the time for the melt of the biodegradable aliphatic aromatic copolyester raw material to reach 30HD hardness under the same state, and further preferably can be 100% shorter; and a better technical effect is achieved.
The invention is further illustrated by the following specific examples.
Detailed Description
The present invention is specifically described by the following examples. It should be noted that the following examples are given solely for the purpose of illustration and are not to be construed as limitations on the scope of the invention, as many insubstantial modifications and variations of the invention may be made by those skilled in the art in light of the above teachings.
[ example 1 ]
The 1, 4-succinic acid, the terephthalic acid, the 1, 4-butanediol, the tetraisopropyl titanate and the pentaerythritol which are used in the invention are CP grade products of national chemical and chemical test companies. In a reaction kettle for completely removing water and oxygen, 1, 4-succinic acid and terephthalic acid respectively account for 50 percent and 50 percent of the molar ratio of the total diacid feeding amount, 1, 4-butanediol is fed in the molar ratio of 105 percent of the total diacid feeding amount, pentaerythritol accounting for 0.25 percent of the total diacid molar ratio is additionally added, and the adding amount of catalyst tetraisopropyl titanate is two ten-thousandth of the total diacid molar ratio. After the feeding is finished, stirring is kept under the protection of inert gas, the temperature of the reaction kettle is slowly increased from 80 ℃ to 215 ℃, the temperature is kept at 215 ℃ for about 2.5 hours, the reaction degree is ensured to be more than 90%, then, a vacuum pump is used for pumping air, the oil bath temperature is increased to 245 ℃, the pumping air is kept for about 2 hours until the stirring torque is constant, and the polymerization step is finished. After the polymerization reaction, the melt was colorless and transparent, extruded through a die having a diameter of about 5mm, cooled in a room-temperature water bath, and cut into cylindrical particles having a length of about 3mm by a pelletizer. Pumping the granules in a vacuum drying oven at 60 deg.C for 4hr, cooling, and packaging.
[ example 2 ]
In a reaction kettle for completely removing water and oxygen, 1, 4-succinic acid and terephthalic acid respectively account for 55 percent and 45 percent of the molar ratio of the total diacid feeding amount, 1, 4-butanediol is fed in the molar ratio of 105 percent of the total diacid feeding amount, pentaerythritol accounting for 0.25 percent of the total diacid molar ratio is additionally added, and the adding amount of catalyst tetraisopropyl titanate is two ten-thousandth of the total diacid molar ratio. After the feeding is finished, stirring is kept under the protection of inert gas, the temperature of the reaction kettle is slowly increased from 80 ℃ to 215 ℃, the temperature is kept at 215 ℃ for about 2.5 hours, the reaction degree is ensured to be more than 90%, then, a vacuum pump is used for pumping air, the oil bath temperature is increased to 245 ℃, the pumping air is kept for about 2 hours until the stirring torque is constant, and the polymerization step is finished. After the polymerization reaction, the melt was colorless and transparent, extruded through a die having a diameter of about 5mm, cooled in a room-temperature water bath, and cut into cylindrical particles having a length of about 3mm by a pelletizer. Pumping the granules in a vacuum drying oven at 60 deg.C for 4hr, cooling, and packaging.
[ example 3]
In a reaction kettle for completely removing water and oxygen, 1, 4-succinic acid and terephthalic acid respectively account for 20 percent and 80 percent of the molar ratio of the total diacid feeding amount, 1, 4-butanediol is fed in the molar ratio of 105 percent of the total diacid feeding amount, pentaerythritol accounting for 0.25 percent of the total diacid molar ratio is additionally added, and the adding amount of catalyst tetraisopropyl titanate is two ten-thousandth of the total diacid molar ratio. After the feeding is finished, stirring is kept under the protection of inert gas, the temperature of the reaction kettle is slowly increased from 80 ℃ to 215 ℃, the temperature is kept at 215 ℃ for about 2.5 hours, the reaction degree is ensured to be more than 90%, then, a vacuum pump is used for pumping air, the oil bath temperature is increased to 245 ℃, the pumping air is kept for about 2 hours until the stirring torque is constant, and the polymerization step is finished. After the polymerization reaction, the melt was colorless and transparent, extruded through a die having a diameter of about 5mm, cooled in a room-temperature water bath, and cut into cylindrical particles having a length of about 3mm by a pelletizer. Pumping the granules in a vacuum drying oven at 60 deg.C for 4hr, cooling, and packaging.
[ example 4 ]
In a reaction kettle for completely removing water and oxygen, 1, 4-succinic acid and terephthalic acid respectively account for 40 percent and 60 percent of the molar ratio of the total diacid feeding amount, 1, 4-butanediol is fed in the molar ratio of 105 percent of the total diacid feeding amount, pentaerythritol accounting for 0.25 percent of the total diacid molar ratio is additionally added, and the adding amount of catalyst tetraisopropyl titanate is two ten-thousandth of the total diacid molar ratio. After the feeding is finished, stirring is kept under the protection of inert gas, the temperature of the reaction kettle is slowly increased from 80 ℃ to 215 ℃, the temperature is kept at 215 ℃ for about 2.5 hours, the reaction degree is ensured to be more than 90%, then, a vacuum pump is used for pumping air, the oil bath temperature is increased to 245 ℃, the pumping air is kept for about 2 hours until the stirring torque is constant, and the polymerization step is finished. After the polymerization reaction, the melt was colorless and transparent, extruded through a die having a diameter of about 5mm, cooled in a room-temperature water bath, and cut into cylindrical particles having a length of about 3mm by a pelletizer. Pumping the granules in a vacuum drying oven at 60 deg.C for 4hr, cooling, and packaging.
[ example 5 ]
The 1, 6-adipic acid used in the invention is a CP grade product of a national chemical industry testing company. In a reaction kettle for completely removing water and oxygen, 1, 6-adipic acid and terephthalic acid respectively account for 50 percent and 50 percent of the molar ratio of the total diacid feeding amount, 1, 4-butanediol is fed in the molar ratio of 105 percent of the total diacid feeding amount, pentaerythritol accounting for 0.25 percent of the total diacid molar ratio is additionally added, and the adding amount of catalyst tetraisopropyl titanate is two ten-thousandth of the total diacid molar ratio. After the feeding is finished, stirring is kept under the protection of inert gas, the temperature of the reaction kettle is slowly increased from 80 ℃ to 215 ℃, the temperature is kept at 215 ℃ for about 2.5 hours, the reaction degree is ensured to be more than 90%, then, a vacuum pump is used for pumping air, the oil bath temperature is increased to 245 ℃, the pumping air is kept for about 2 hours until the stirring torque is constant, and the polymerization step is finished. After the polymerization reaction, the melt was colorless and transparent, extruded through a die having a diameter of about 5mm, cooled in a room-temperature water bath, and cut into cylindrical particles having a length of about 3mm by a pelletizer. Pumping the granules in a vacuum drying oven at 60 deg.C for 4hr, cooling, and packaging.
[ example 6 ]
In a reaction kettle for completely removing water and oxygen, 1, 6-adipic acid and terephthalic acid account for 20 percent and 80 percent of the molar ratio of the total diacid feeding amount respectively, 1, 4-butanediol is fed in the molar ratio of 105 percent of the total diacid feeding amount, pentaerythritol accounting for 0.25 percent of the total diacid molar ratio is additionally added, and the adding amount of catalyst tetraisopropyl titanate is two ten-thousandth of the total diacid molar ratio. After the feeding is finished, stirring is kept under the protection of inert gas, the temperature of the reaction kettle is slowly increased from 80 ℃ to 215 ℃, the temperature is kept at 215 ℃ for about 2.5 hours, the reaction degree is ensured to be more than 90%, then, a vacuum pump is used for pumping air, the oil bath temperature is increased to 245 ℃, the pumping air is kept for about 2 hours until the stirring torque is constant, and the polymerization step is finished. After the polymerization reaction, the melt was colorless and transparent, extruded through a die having a diameter of about 5mm, cooled in a room-temperature water bath, and cut into cylindrical particles having a length of about 3mm by a pelletizer. Pumping the granules in a vacuum drying oven at 60 deg.C for 4hr, cooling, and packaging.
[ example 7 ]
The chain extender used in the invention is the product of BASF company of Germany with the trade name of
ADR 4368. No. 5 paraffin oil used in the invention is purchased from Hangzhou oil refineries of the Chinese petrochemical group. The PBST particles prepared in example 1, the PBST particles prepared in example 3, the chain extender and the paraffin oil were thoroughly mixed in a mass ratio of 1000:20:5:5, and then the mixture was treated with PolyLab HAAKE from Thermo Fisher scientific Co., USATMRheomex OS PTW16 co-rotating twin-screw extruder (screw diameter 16mm, length-diameter ratio 40) was extruded for granulation. The extruder comprises 11 sections from a feeding port to a neck mold, wherein the number of the sections is 1-11, the section 1 only plays a role of feeding and is not heated, and the temperatures of the sections 2-11 of the extruder are respectively set as follows: 180 ℃,200 ℃,200 ℃,200 ℃,200 ℃,200 ℃,200 ℃,200 ℃, 180 ℃ and the screw speed is set at 200 rpm. The mixed raw materials are fed to the 1 st section of the extruder by a volumetric feeder attached to the extruder, and the feeding speed is about 2000 g/hr. The extruder was equipped with a circular die having a diameter of 3mm, from which the sample strips were extruded (essentially transparent), passed through a cold water bath at room temperature of 1m long and after about 18s were crystallization-hardened to about 30 HD.
[ example 8 ]
The PBST particles prepared in example 2, the PBST particles prepared in example 4, the chain extender and the paraffin oil were mixed thoroughly in a mass ratio of 1000:20:5:5, and then the mixture was treated with PolyLabHAAKE from Thermo Fisher scientific Co., USATMRheomex OS PTW16 co-rotating twin-screw extruder (screw diameter 16mm, length-diameter ratio 40) was extruded for granulation. The extruder comprises 11 sections from a feeding port to a neck mold, wherein the number of the sections is 1-11, the section 1 only plays a role of feeding and is not heated, and the temperatures of the sections 2-11 of the extruder are respectively set as follows: 180 ℃,200 ℃,200 ℃,200 ℃,200 ℃,200 ℃,200 ℃,200 ℃, 180 ℃ and the screw speed is set at 200 rpm. The mixed raw materials are fed to the 1 st section of the extruder by a volumetric feeder attached to the extruder, and the feeding speed is about 2000 g/hr. The extruder was equipped with a circular die having a diameter of 3mm, from which the sample strips were extruded (colorless and transparent), passed through a cold water bath at room temperature of 1m long and crystallized and hardened to about 30HD after about 25 seconds.
[ example 9 ]
The PBAT particles prepared in example 5, the PBAT particles prepared in example 6, the chain extender and the paraffin oil were thoroughly mixed in a mass ratio of 1000:20:5:5, and then the mixture was treated with PolyLabHAAKE from Thermo Fisher scientific Co., USATMRheomex OS PTW16 co-rotating twin-screw extruder (screw diameter 16mm, length-diameter ratio 40) was extruded for granulation. The extruder comprises 11 sections from a feeding port to a neck mold, wherein the number of the sections is 1-11, the section 1 only plays a role of feeding and is not heated, and the temperatures of the sections 2-11 of the extruder are respectively set as follows: 180 ℃,200 ℃,200 ℃,200 ℃,200 ℃,200 ℃,200 ℃,200 ℃, 180 ℃ and the screw speed is set at 200 rpm. The mixed raw materials are fed to the 1 st section of the extruder by a volumetric feeder attached to the extruder, and the feeding speed is about 2000 g/hr. The extruder was equipped with a circular die having a diameter of 3mm, from which the sample strips were extruded (colorless and transparent), passed through a cold water bath at room temperature of 1m long and crystallized and hardened to about 30HD after about 21 seconds.
Comparative example 1
The PBST particles prepared in example 1 were thoroughly mixed with the chain extender and paraffin oil described above at a mass ratio of 1000:5:5, and then treated with PolyLab HAAKE from Thermo Fisher scientific Co., USATMRheomex OS PTW16 same asExtruding and granulating the mixture to a double-screw extruder (the diameter of a screw is 16mm, and the length-diameter ratio is 40). The extruder comprises 11 sections from a feeding port to a neck mold, wherein the number of the sections is 1-11, the section 1 only plays a role of feeding and is not heated, and the temperatures of the sections 2-11 of the extruder are respectively set as follows: 180 ℃,200 ℃,200 ℃,200 ℃,200 ℃,200 ℃,200 ℃,200 ℃, 180 ℃ and the screw speed is set at 200 rpm. The mixed raw materials are fed to the 1 st section of the extruder by a volumetric feeder attached to the extruder, and the feeding speed is about 2000 g/hr. The extruder was equipped with a circular die having a diameter of 3mm, from which the sample strips were extruded (colorless and transparent), passed through a cold water bath at room temperature of 1m long and crystallized and hardened to about 30HD after about 40 seconds.
Comparative example 2
The PBST particles prepared in example 2 were thoroughly mixed with the chain extender and paraffin oil described above at a mass ratio of 1000:5:5, and then treated with PolyLab HAAKE from Thermo Fisher scientific Co., USATMRheomex OS PTW16 co-rotating twin-screw extruder (screw diameter 16mm, length-diameter ratio 40) was extruded for granulation. The extruder comprises 11 sections from a feeding port to a neck mold, wherein the number of the sections is 1-11, the section 1 only plays a role of feeding and is not heated, and the temperatures of the sections 2-11 of the extruder are respectively set as follows: 180 ℃,200 ℃,200 ℃,200 ℃,200 ℃,200 ℃,200 ℃,200 ℃, 180 ℃ and the screw speed is set at 200 rpm. The mixed raw materials are fed to the 1 st section of the extruder by a volumetric feeder attached to the extruder, and the feeding speed is about 2000 g/hr. The extruder was equipped with a circular die having a diameter of 3mm, from which the sample strips were extruded (colorless and transparent), passed through a cold water bath at room temperature of 1m long and crystallized and hardened to about 30HD after about 60 seconds.
Comparative example 3
The PBAT particles prepared in example 5 were thoroughly mixed with the chain extender and paraffin oil described above at a mass ratio of 1000:5:5, and then treated with PolyLab HAAKE from Thermo Fisher scientific Co., USATMRheomex OS PTW16 co-rotating twin-screw extruder (screw diameter 16mm, length-diameter ratio 40) was extruded for granulation. The extruder comprises 11 sections from a feeding port to a neck mold, wherein the number of the sections is 1-11, the section 1 only plays a role of feeding and is not heated, and the temperatures of the sections 2-11 of the extruder are respectively set as follows: 180 ℃,200 ℃,220 ℃,240 ℃,260 ℃,260 ℃,240 ℃,240 ℃,220 ℃ and 200 ℃, the screw speed was set at 200 rpm. The mixed raw materials are fed to the 1 st section of the extruder by a volumetric feeder attached to the extruder, and the feeding speed is about 2000 g/hr. The extruder was equipped with a circular die having a diameter of 3mm, from which the sample strips were extruded (colorless and transparent), passed through a cold water bath at room temperature of 1m long and then crystallized and hardened to about 30HD after about 45 seconds.
Claims (10)
1. An aliphatic aromatic copolyester blend comprises the following components in parts by mass:
(1) 90-99 parts of biodegradable aliphatic aromatic copolyester;
(2) 1-10 parts of aliphatic aromatic polyester with low aliphatic diacid content;
wherein the biodegradable aliphatic aromatic copolyester and the aliphatic aromatic polyester with low aliphatic diacid content contain the same repeating units.
2. The aliphatic aromatic copolyester blend according to claim 1, wherein the biodegradable aliphatic aromatic copolyester comprises an aliphatic diacid or aliphatic diacid derivative segment, an aromatic diacid or aromatic diacid derivative segment and at least one aliphatic diol segment; the mole fraction of aliphatic diacid in the total diacid is 50-59%.
3. The aliphatic aromatic copolymer ester blend according to claim 2, wherein the biodegradable aliphatic aromatic copolymer ester is at least one of polybutylene succinate-co-terephthalate and polybutylene adipate-co-terephthalate.
4. The aliphatic aromatic copolyester blend according to claim 1, wherein the aliphatic aromatic copolyester with a low aliphatic diacid content comprises segments of aliphatic diacid or aliphatic diacid derivative, segments of aromatic diacid or aromatic diacid derivative and segments of at least one aliphatic diol; wherein the molar fraction of the aliphatic diacid in the total diacid is 10-40 percent and is lower than the content of the aliphatic diacid in the biodegradable aliphatic aromatic copolyester.
5. The aliphatic aromatic copolyester blend according to claim 4, wherein the aliphatic aromatic copolyester with low aliphatic diacid content is selected from at least one of polybutylene succinate-co-terephthalate and polybutylene adipate-co-terephthalate.
6. The aliphatic aromatic copolyester blend according to claim 1, wherein the aliphatic aromatic copolyester blend further comprises 0 to 5 parts of a functional additive; preferably, the functional auxiliary agent comprises at least one of a chain extender, a compatilizer and a plasticizer.
7. The aliphatic aromatic copolyester blend according to claim 6, wherein the time for the melt of the aliphatic aromatic copolyester blend to reach 30HD hardness after being cooled by a normal temperature water bath is at least 50% shorter than the time for the melt of the biodegradable aliphatic aromatic copolyester raw material to reach 30HD hardness under the same condition.
8. A method for preparing the aliphatic aromatic copolyester blend according to any one of claims 1 to 7, comprising the following steps:
and (2) preparing the biodegradable aliphatic aromatic copolyester, the aliphatic aromatic polyester with low aliphatic diacid content and optional functional auxiliary agent by a blending method according to the mass parts to obtain the aliphatic aromatic copolyester blend.
9. The method for producing an aliphatic aromatic copolyester blend according to claim 8, wherein the blending method is at least one of a solution blending method and a melt blending method, more preferably a melt blending method, and still more preferably a melt blending method using a twin-screw extruder.
10. Use of an aliphatic aromatic copolyester blend according to any one of claims 1 to 7.
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| IT202100002135A1 (en) * | 2021-02-02 | 2022-08-02 | Novamont Spa | BRANCHED POLYESTERS FOR EXTRUSION COATING |
| WO2023236862A1 (en) * | 2022-06-06 | 2023-12-14 | 惠州博科环保新材料有限公司 | Method for synthesizing biodegradable block copolyester and block copolyester |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| IT202100002135A1 (en) * | 2021-02-02 | 2022-08-02 | Novamont Spa | BRANCHED POLYESTERS FOR EXTRUSION COATING |
| WO2022167410A1 (en) * | 2021-02-02 | 2022-08-11 | Novamont S.P.A. | Process for branched polyesters for extrusion coating and related products |
| WO2023236862A1 (en) * | 2022-06-06 | 2023-12-14 | 惠州博科环保新材料有限公司 | Method for synthesizing biodegradable block copolyester and block copolyester |
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