CN114479394B - Full-biodegradable straw and preparation method thereof - Google Patents
Full-biodegradable straw and preparation method thereof Download PDFInfo
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- CN114479394B CN114479394B CN202111559002.0A CN202111559002A CN114479394B CN 114479394 B CN114479394 B CN 114479394B CN 202111559002 A CN202111559002 A CN 202111559002A CN 114479394 B CN114479394 B CN 114479394B
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2201/06—Biodegradable
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Abstract
The invention provides a full-biodegradation straw and a preparation method thereof, wherein the full-biodegradation straw with good mechanical property is obtained by blending a carbon dioxide-based polymer and modified polylactic acid; refining carbon dioxide-based polyol with a carbonate and ether coexisting structure, and then connecting tertiary amine to the end group of a polyurethane chain to prepare carbon dioxide-based polyurethane; introducing hydroxymethyl side chain groups onto a main chain of the polybutyrolactam through a grafting reaction to prepare modified polylactic acid, extruding a carbon dioxide-based polymer and the modified polylactic acid through a micro-nano co-extrusion device to obtain a layered microstructure, so that the fully biodegradable straw has high phase continuity, and the thermal stability, the high temperature resistance and the moisture resistance of the straw are synergistically improved; the invention can obtain the full-biodegradable straw with good mechanical property, high thermal stability, moisture resistance and no peculiar smell under the condition of not adding a compatibilizer due to the limitation of raw materials and a process.
Description
Technical Field
The invention relates to the field of straw preparation, in particular to a full-biodegradation straw and a preparation method thereof.
Background
In recent years, with the development of economy and social progress, the use of plastic products such as disposable tableware has become a part of daily life, and although it brings convenience to people's life, it also causes serious environmental problems such as white pollution, because these disposable tableware are not only difficult to recycle but also difficult to degrade, the straw is a common disposable tableware.
In order to respond to the policy of plastic limitation and plastic reduction, most of coffee and milk tea beverage shops and takeoffs at present change to provide paper straws and degradable straws. At present, the paper straws are mainly used as straws in beverage shops on the market, but the paper pulp wood consumed by the paper straws is large in quantity, and the paper straws are easy to damp and mildew in storage, are flat after being pinched, and are easy to bend and influence the mouthfeel of beverages when meeting high temperature. Most of the existing degradable plastic straws can not be completely degraded, and have the defects of low mechanical property, peculiar smell, poor moisture resistance, unsatisfactory high temperature resistance and the like.
Disclosure of Invention
The invention aims to provide a full-biodegradable straw and a preparation method thereof, and aims to solve the problems in the prior art.
In order to solve the technical problems, the invention provides the following technical scheme:
the preparation method of the full-biodegradable straw comprises the following steps: mixing the raw materials, adding the mixture into a double-screw extruder with a cylinder temperature of 160-180 ℃ and a die head temperature of 170 ℃, blending, extruding and granulating, cooling to 18-25 ℃, drawing a pipe by using a pipe drawing machine, and then carrying out heat treatment at 105 ℃ for 5min to obtain a full-biodegradation straw;
the raw materials comprise the following components in parts by weight: 3-8 parts of carbon dioxide-based polymer, 52-65 parts of modified polylactic acid, 30-40 parts of polybutylene succinate, 0.3-0.5 part of ethylene bis stearamide, 0.680-0.3 part of compatibilizer and 0.05-0.3 part of stearic acid amide. The carbon dioxide-based polymer is obtained by compounding carbon dioxide-based PPC and carbon dioxide polyurethane in a weight part ratio of 9:1, and the brand of the carbon dioxide-based PPC is PPC/Henan Nanyang Tianguan.
With the enhancement of the attention of people to health and environmental protection problems, the reduction of the emission of volatile organic compounds and harmful air pollutants into the atmosphere is of great importance to the treatment of environmental pollution; the replacement of solvent-borne polyurethanes by aqueous polyurethanes is one of the important measures to achieve low pollutant emissions. The invention responds to the requirement of green production, and selects green degradable raw materials to prepare the full-biodegradable straw.
Further, the preparation method of the carbon dioxide-based polyurethane comprises the following steps:
(1) Stirring zinc sulfate and deionized water at 40 ℃, dropwise adding a potassium cobalt cyanide aqueous solution into the zinc sulfate solution within 40min through a constant-pressure dropping funnel, centrifuging the suspension for 2min at a centrifugal speed of 5500rpm after ultrasonic stirring, washing the separated slurry with a mixed solution of the deionized water and tert-butyl alcohol, centrifuging the suspension for 2min at the centrifugal speed of 5500rpm, continuously washing the separated slurry with the mixed solution, gradually increasing the proportion of the tert-butyl alcohol to the water in the mixed solution until pure tert-butyl alcohol is used as a detergent, centrifuging the solid, and drying the solid at 40 ℃ in vacuum to obtain the zinc-cobalt-based double metal cyanide;
(2) Adding zinc-cobalt-based double metal cyanide, cyclopentane epoxide and isophthalic acid into a reaction kettle, then introducing carbon dioxide gas, heating to 75 ℃ for reaction for 7 hours, cooling the reaction kettle to 20-25 ℃ after the reaction is finished, releasing the gas in the reaction kettle, dissolving the product in deionized water, and filtering to obtain carbon dioxide-based polyol;
(3) And (2) dehydrating the carbon dioxide-based polyol for 2h under reduced pressure in an oil bath at the temperature of 80 ℃, adding isophorone diisocyanate and 2,2-dimethylolpropionic acid under the atmosphere of nitrogen, mixing and stirring, then adding 1,4 butanediol, dibutyltin dilaurate and 2-butanone, mixing and stirring, then neutralizing with triethylamine for 30min at the temperature of 30 ℃, and obtaining the carbon dioxide-based polyurethane through reduced pressure distillation in a water bath at the temperature of 40 ℃.
In the zinc sulfate solution, the volume ratio of the deionized water to the tertiary butanol is 2:1; the mass ratio of the carbon dioxide-based polyol to the isophorone diisocyanate to the 1,4 butanediol to the 3-methylamino-1,2-propanediol is (1.8-6.3) to (0.8-6.6) of 50.
When the zinc-cobalt-based double metal cyanide is used as a catalyst, the carbon dioxide-based polyol must be dissolved in deionized water and a solvent for many times, and the product is filtered to remove the zinc-cobalt-based double metal cyanide, and in the process of preparing the carbon dioxide-based polyol, when detecting the residue of the zinc-cobalt-based double metal cyanide, the amount of the residue of the zinc-cobalt-based double metal cyanide must be less than 0.5ppm because the prepared straw conforms to the national food safety standard.
Anionic polyurethane is mostly selected for preparing carbon dioxide-based polyurethane by the prior art, and because the water dispersibility of the water-based cationic polyurethane is far lower than that of the anionic polyurethane, excessive cationic hydrophilic chain extender must be used in the prior preparation process to make up for the defect, so that the water resistance is poor.
According to the invention, the water-based cationic polyurethane is selected to prepare the carbon dioxide-based polyurethane, the carbon dioxide-based polyol synthesized based on the telomerization reaction of carbon dioxide and cyclopentane epoxide has a structure of coexisting carbonate and ether, the carbon dioxide-based polyol is refined for many times, and the zinc-cobalt-based double metal cyanide catalyst is removed;
the invention does not prepare a hydrophilic chain extender with a novel structure, and improves the neutralization effect between the tertiary amine group and acid on the polyurethane chain and the hydrophilicity and the emulsification efficiency of the hydrophilic group by grafting the tertiary amine on the end group of the polyurethane chain. The 3-methylamino-1,2-propylene glycol terminated aqueous cationic polyurethane is prepared by using the carbon dioxide-based polyol, the excellent storage stability of the prepared aqueous cationic carbon dioxide-based polyurethane is ensured, the using amount of the hydrophilic chain extender can be reduced to 0-0.5wt%, and in order to obtain the 3-methylamino-1,2-propylene glycol terminated aqueous cationic polyurethane, the adding amount and the adding sequence of a reagent can not be adjusted, so that the generation of side reaction is reduced;
the reactivity between the micromolecule acid and the tertiary amine group is optimized, the carbon dioxide-based polyol with the cationic hydrophilic group at the end group is prepared, when the hydrophilic group is positioned at the end group, the hydrophilicity and the stability are greatly improved, so that the straw has excellent hydrolysis resistance and oxidation resistance, and simultaneously the straw shows outstanding thermal stability and widely adjustable mechanical properties.
Further, the preparation method of the modified polylactic acid comprises the following steps: heating polybutyrolactam and formic acid to 60 ℃ to obtain a polybutyrolactam formic acid solution, dissolving trioxymethylene in the formic acid, adding the solution into the prepared polybutyrolactam formic acid solution, heating to 60 ℃ to react for 1h, precipitating by using acetone, and performing vacuum drying for 3-5 times by suction filtration to obtain hydroxylated polybutyrolactam; and (3) blending and extruding the hydroxylated polybutyrolactam and the polylactic acid to obtain the modified polylactic acid.
Further, the molar ratio of the polybutyrolactam to the formic acid in the solution of the polybutyrolactam is 5; in the trioxymethylene mixed solution, the mol ratio of trioxymethylene to formic acid is (2-3) to 70; the mass ratio of the hydroxylated polybutyrolactam to the polylactic acid is 1:8.
Polylactic acid is a degradable material with wide sources, but hydrophobic groups exist among molecules, so that the polylactic acid has good water vapor barrier property, but low toughness, poor oxygen resistance and poor high temperature resistance; the bio-based polybutyrolactam is bio-based degradable nylon, has good mechanical property, oxygen resistance and high temperature resistance, but has stronger hygroscopicity and poor water resistance due to higher amido bond content in a molecular chain, and the high-density amido bonds in a chain segment cause that the internal hydrogen bonding force is very strong and is difficult to damage due to the structural characteristics of the polybutyrolactam. When the materials are directly blended, a phase separation structure is easily generated, so that the blended materials have defects;
according to the invention, hydroxymethyl side chain groups are introduced to a main chain of the polybutyrolactam through a grafting reaction, the cohesive force among molecular chains is destroyed, the mobility is enhanced, the compatibility of the polybutyrolactam and the polylactic acid is improved, and the prepared straw not only has biodegradability, but also synergistically improves the high temperature resistance and the moisture resistance of the straw.
Further, the preparation method of the full-biodegradation straw comprises the following steps:
s1: dividing the carbon dioxide-based polymer into 2 parts according to the weight part ratio of 99;
s2: melting and blending the carbon dioxide-based polymer B and the modified polylactic acid by a double-screw extruder, extruding, granulating and drying to obtain a material a; melting and blending the carbon dioxide-based polymer A, polybutylene succinate, ethylene bis-stearamide and stearic acid amide by a double-screw extruder, extruding, granulating and drying to obtain a material b;
s3: and (b) preparing a full-biodegradation straw from the a and the b by using a micro-nano co-extrusion device.
Furthermore, the micro-nano co-extrusion device consists of a double-screw extruder, a connector, a distributor, a layer multiplier I, a layer multiplier II and an extrusion die.
Further, in the micro-nano co-extrusion device, melt plasticized and melted by a double-screw extruder is subjected to connector and distributor to obtain 4 layers of melt which are alternately distributed, the 4 layers of melt enter a layer multiplier I and are divided into 4 strands of melt, the 4 strands of melt are gradually changed into vertical arrangement from horizontal arrangement in a runner, then confluence is carried out to obtain 16 layers of melt, the 16 layers of melt are subjected to layer multiplier II to obtain 64 layers of melt, the melt is cooled to 18-25 ℃ after passing through an extrusion die, and then a tube drawing machine is adopted to draw a tube, so that the fully biodegradable straw is obtained.
Further, the temperatures from the cylinder zone of the twin-screw extruder to the extrusion die were 175 ℃, 185 ℃, 195 ℃, 185 ℃.
The invention designs a micro-nano co-extrusion device, which comprises the following steps of firstly dividing a carbon dioxide-based polymer into 2 parts according to the weight part ratio of 99 to 1, obtaining a material a by a double-screw extruder from 1% of a carbon dioxide-based polymer B and modified polylactic acid, and increasing the capacity of the modified polylactic acid by using the 1% of the carbon dioxide-based polymer B to cooperatively improve the stability of the modified polylactic acid and the thermal stability of a straw, so that the high-temperature-resistant, moisture-resistant and odorless fully biodegradable straw with good mechanical property can be obtained without additionally adding a capacity increasing agent.
The full-biodegradation straw obtained through the micro-nano co-extrusion device has a layered microstructure, so that the full-biodegradation straw has high phase continuity, macromolecular chains at interfaces of adjacent layers are mutually diffused and intertwined, the heterogeneous nucleation effect between the carbon dioxide-based polymer and the modified polylactic acid is enhanced, more active sites are generated, and the crystallization performance and the thermal stability of the full-biodegradation straw are higher than those of the full-biodegradation straw obtained through direct blending extrusion.
The invention has the beneficial effects that:
the invention provides a full-biodegradable straw and a preparation method thereof, wherein the full-biodegradable straw with good temperature resistance is obtained by limiting the added component and process design, co-extruding a carbon dioxide-based polymer and modified polylactic acid and then annealing;
according to the invention, carbon dioxide-based polyol with a structure of coexistence of carbonate and ether is refined, and then tertiary amine is connected to the end group of a polyurethane chain to prepare carbon dioxide-based water-based cationic polyurethane, so that the straw has excellent water resistance, oxidation resistance and thermal stability; according to the invention, hydroxymethyl side chain groups are introduced to a main chain of the polybutyrolactam through a grafting reaction, so that the compatibility of the polybutyrolactam and the polylactic acid is improved, and the modified polylactic acid and the carbon dioxide-based polymer synergistically improve the high temperature resistance and the moisture resistance of the straw;
according to the micro-nano co-extrusion device, the layered microstructure obtained by the micro-nano co-extrusion device enables the full-biodegradation straw to have high phase continuity, macromolecular chains at interfaces of adjacent layers are mutually diffused and intertwined, the heterogeneous nucleation effect between the carbon dioxide-based polymer and the modified polylactic acid is enhanced, more active sites are generated, and the thermal stability of the straw is greatly improved; according to the invention, the full-biodegradable straw with good mechanical property, high thermal stability, moisture resistance and no peculiar smell is obtained by limiting the raw materials and the process without additionally adding a compatibilizer and annealing treatment.
Detailed Description
The technical solutions in the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that, if directional indications such as up, down, left, right, front, and back … … are involved in the embodiment of the present invention, the directional indications are only used for explaining a specific posture, such as a relative positional relationship between components, a motion situation, and the like, and if the specific posture changes, the directional indications also change accordingly. In addition, technical solutions between various embodiments may be combined with each other, but must be realized by a person skilled in the art, and when the technical solutions are contradictory or cannot be realized, such a combination should not be considered to exist, and is not within the protection scope of the present invention.
The technical solutions of the present invention are further described in detail with reference to specific examples, which should be understood that the following examples are only illustrative of the present invention and are not intended to limit the present invention.
Example 1
The preparation method of the full-biodegradable straw comprises the following steps: mixing the raw materials, adding the mixture into a double-screw extruder with a cylinder temperature of 160 ℃ and a die head temperature of 170 ℃, blending, extruding and granulating, cooling to 18 ℃, drawing a pipe by using a pipe drawing machine, and then carrying out heat treatment at 105 ℃ for 5min to obtain a full-biodegradable straw;
the raw materials comprise the following components in parts by weight: 3 parts of carbon dioxide-based polymer, 65 parts of modified polylactic acid, 30 parts of polybutylene succinate, 0.3 part of ethylene bis stearamide, 3242 parts of compatibilizer 44680.1 parts and 0.05 part of stearic acid amide; the carbon dioxide-based polymer is obtained by compounding 2.7 parts of carbon dioxide-based PPC and 0.3 part of carbon dioxide-based polyurethane, the grade of the carbon dioxide-based PPC is PPC/Henan Yang Tian crown, and the length-diameter ratio L/D of the screw is 52;
the preparation method of the carbon dioxide-based polyurethane comprises the following steps:
(1) Stirring 0.42mol of zinc sulfate, 300mL of deionized water and 150mL of tert-butyl alcohol at 40 ℃, dropwise adding 100mL of a 0.20mol/L potassium cobalt cyanide aqueous solution into the zinc sulfate solution within 40min through a constant-pressure dropping funnel, centrifuging the suspension for 2min at a centrifugal speed of 5500rpm after ultrasonic stirring, washing the separated slurry with a deionized water and tert-butyl alcohol mixed solution, centrifuging the suspension for 2min at a centrifugal speed of 5500rpm, continuously washing the separated slurry with the mixed solution, gradually increasing the proportion of tert-butyl alcohol to water in the mixed solution until pure tert-butyl alcohol is used as a washing agent, centrifuging the solid, and drying under vacuum at 40 ℃ to obtain the zinc-cobalt-based double metal cyanide;
(2) Adding 35g of zinc-cobalt-based double metal cyanide, 77kg of cyclopentane epoxide and 3kg of isophthalic acid into a reaction kettle, then introducing carbon dioxide gas, introducing the carbon dioxide gas under the pressure of 2MPa, heating to 75 ℃ for reaction for 7 hours, cooling the reaction kettle to 20 ℃ after the reaction is finished, releasing the gas in the kettle, dissolving the gas in deionized water, filtering the product, and removing the zinc-cobalt-based double metal cyanide to obtain carbon dioxide-based polyol;
(3) 50g of carbon dioxide-based polyol is dehydrated for 2 hours under reduced pressure in an oil bath at the temperature of 80 ℃, under the nitrogen atmosphere, 22g of isophorone diisocyanate and 1.8g of 1,4 butanediol are added for mixing and stirring, then 0.8g of 3-methylamino-1,2-propanediol, 1g of dibutyltin dilaurate and 0.05g of 2-butanone are added for mixing and stirring, then 0.5g of triethylamine is used for neutralization for 30 minutes at the temperature of 30 ℃, and carbon dioxide-based polyurethane is obtained by reduced pressure distillation in a water bath at the temperature of 40 ℃;
the preparation method of the modified polylactic acid comprises the following steps: heating 25mmol of polybutyrolactam and 19.7g of formic acid to 60 ℃ to obtain a formic acid solution of polybutyrolactam, mixing 2mmol of trioxymethylene and 70mmol of formic acid to obtain a trioxymethylene mixed solution, adding the trioxymethylene mixed solution into the prepared formic acid solution of polybutyrolactam, heating to 60 ℃ to react for 1 hour, precipitating by using acetone, and performing suction filtration for 3 times to obtain hydroxylated polybutyrolactam after vacuum drying; 50g of hydroxylated polybutyrolactam and 400g of polylactic acid are blended and extruded to obtain the modified polylactic acid.
Example 2
The preparation method of the full-biodegradable straw comprises the following steps: mixing the raw materials, adding the mixture into a double-screw extruder with a cylinder temperature of 170 ℃ and a die head temperature of 175 ℃, blending, extruding and granulating, cooling to 20 ℃, drawing a pipe by using a pipe drawing machine, and then carrying out heat treatment at 105 ℃ for 5min to obtain the full-biodegradable straw.
The raw materials comprise the following components in parts by weight: 6 parts of carbon dioxide-based polymer, 60 parts of polylactic acid, 32 parts of polybutylene succinate, 0.4 part of ethylene bis stearamide, 3242 parts of compatibilizer 44680.2 parts and 0.1 part of stearic acid amide; the carbon dioxide-based polymer is obtained by compounding 5.4 parts of carbon dioxide-based PPC and 0.6 part of carbon dioxide-based polyurethane, the grade of the carbon dioxide-based PPC is PPC/Henan Yang Tian crown, and the length-diameter ratio L/D of the screw is 52;
the preparation method of the carbon dioxide-based polyurethane comprises the following steps:
(1) Stirring 0.42mol of zinc sulfate, 300mL of deionized water and 150mL of tert-butyl alcohol at 40 ℃, dropwise adding 100mL of a 0.20mol/L potassium cobalt cyanide aqueous solution into the zinc sulfate solution through a constant-pressure dropping funnel within 40min, centrifuging the suspension at a centrifugal speed of 5500rpm for 2min after ultrasonic stirring, washing the separated slurry with a deionized water and tert-butyl alcohol mixed solution, centrifuging the suspension at a centrifugal speed of 5500rpm for 2min, continuously washing the separated slurry with the mixed solution, gradually increasing the proportion of tert-butyl alcohol to water in the mixed solution until pure tert-butyl alcohol is used as a washing agent, centrifuging the solid, and drying at 40 ℃ in vacuum to obtain the zinc-cobalt-based double metal cyanide;
(2) Adding 35g of zinc-cobalt-based double metal cyanide, 77kg of cyclopentane epoxide and 3kg of isophthalic acid into a reaction kettle, then introducing carbon dioxide gas, introducing the carbon dioxide gas under the pressure of 2MPa, heating to 75 ℃ for reaction for 7 hours, cooling the reaction kettle to 20 ℃ after the reaction is finished, releasing the gas in the kettle, dissolving the gas in deionized water, filtering the product, and removing the zinc-cobalt-based double metal cyanide to obtain carbon dioxide-based polyol;
(3) 50g of carbon dioxide-based polyol is dehydrated for 2h under reduced pressure in an oil bath at the temperature of 80 ℃, 22g of isophorone diisocyanate and 1.8g of 1,4 butanediol are added to be mixed and stirred under the atmosphere of nitrogen, then 0.8g of 3-methylamino-1,2-propanediol, 1g of dibutyltin dilaurate and 0.05g of 2-butanone are added to be mixed and stirred, then 0.5g of triethylamine is used for neutralization for 30min at the temperature of 30 ℃, and carbon dioxide-based polyurethane is obtained by reduced pressure distillation in a water bath at the temperature of 40 ℃;
the preparation method of the modified polylactic acid comprises the following steps: heating 25mmol of polybutyrolactam and 19.7g of formic acid to 60 ℃ to obtain a formic acid solution of the polybutyrolactam, mixing 2mmol of trioxymethylene and 70mmol of formic acid to obtain a trioxymethylene mixed solution, then adding the trioxymethylene mixed solution into the prepared formic acid solution of the polybutyrolactam, heating to 60 ℃ to react for 1h, precipitating by using acetone, and carrying out suction filtration for 3 times of vacuum drying to obtain hydroxylated polybutyrolactam; 50g of hydroxylated polybutyrolactam and 400g of polylactic acid are blended and extruded to obtain the modified polylactic acid.
Example 3
The preparation method of the full-biodegradable straw comprises the following steps: mixing the raw materials, adding the mixture into a double-screw extruder with a cylinder temperature of 180 ℃ and a die head temperature of 170 ℃, blending, extruding and granulating, cooling to 25 ℃, drawing a pipe by using a pipe drawing machine, and then carrying out heat treatment at 105 ℃ for 5min to obtain the fully biodegradable straw.
The raw materials comprise the following components in parts by weight: 8 parts of carbon dioxide-based polymer, 50 parts of polylactic acid, 40 parts of polybutylene succinate, 0.5 part of ethylene bis stearamide, 8978 parts of compatibilizer zxft 8978 parts, and 0.3 part of stearic acid amide; the carbon dioxide-based polymer is obtained by compounding 7.2 parts of carbon dioxide-based PPC and 0.8 part of carbon dioxide-based polyurethane, the grade of the carbon dioxide-based PPC is PPC/Henan Yang Tian crown, and the length-diameter ratio L/D of the screw is 52;
the preparation method of the carbon dioxide-based polyurethane comprises the following steps:
(1) Stirring 0.42mol of zinc sulfate, 300mL of deionized water and 150mL of tert-butyl alcohol at 40 ℃, dropwise adding 100mL of a 0.20mol/L potassium cobalt cyanide aqueous solution into the zinc sulfate solution through a constant-pressure dropping funnel within 40min, centrifuging the suspension at a centrifugal speed of 5500rpm for 2min after ultrasonic stirring, washing the separated slurry with a deionized water and tert-butyl alcohol mixed solution, centrifuging the suspension at a centrifugal speed of 5500rpm for 2min, continuously washing the separated slurry with the mixed solution, gradually increasing the proportion of tert-butyl alcohol to water in the mixed solution until pure tert-butyl alcohol is used as a washing agent, centrifuging the solid, and drying at 40 ℃ in vacuum to obtain the zinc-cobalt-based double metal cyanide;
(2) Adding 35g of zinc-cobalt-based double metal cyanide, 77kg of cyclopentane epoxide and 3kg of isophthalic acid into a reaction kettle, then introducing carbon dioxide gas, introducing the carbon dioxide gas under the pressure of 2MPa, heating to 75 ℃ for reaction for 7 hours, cooling the reaction kettle to 20 ℃ after the reaction is finished, releasing the gas in the kettle, dissolving the gas in deionized water, filtering the product, and removing the zinc-cobalt-based double metal cyanide to obtain carbon dioxide-based polyol;
(3) 50g of carbon dioxide-based polyol is dehydrated for 2h under reduced pressure in an oil bath at the temperature of 80 ℃, 22g of isophorone diisocyanate and 1.8g of 1,4 butanediol are added to be mixed and stirred under the atmosphere of nitrogen, then 0.8g of 3-methylamino-1,2-propanediol, 1g of dibutyltin dilaurate and 0.05g of 2-butanone are added to be mixed and stirred, then 0.5g of triethylamine is used for neutralization for 30min at the temperature of 30 ℃, and carbon dioxide-based polyurethane is obtained by reduced pressure distillation in a water bath at the temperature of 40 ℃;
the preparation method of the modified polylactic acid comprises the following steps: heating 25mmol of polybutyrolactam and 19.7g of formic acid to 60 ℃ to obtain a formic acid solution of the polybutyrolactam, mixing 2mmol of trioxymethylene and 70mmol of formic acid to obtain a trioxymethylene mixed solution, then adding the trioxymethylene mixed solution into the prepared formic acid solution of the polybutyrolactam, heating to 60 ℃ to react for 1h, precipitating by using acetone, and carrying out suction filtration for 3 times of vacuum drying to obtain hydroxylated polybutyrolactam; 50g of hydroxylated polybutyrolactam and 400g of polylactic acid are blended and extruded to obtain the modified polylactic acid.
Example 4
A preparation method of a full-biodegradation straw comprises the following steps:
s1: dividing the carbon dioxide-based polymer into 2 parts according to the weight part ratio of 99 to 1, wherein the carbon dioxide-based polymer is 0.297 part of carbon dioxide-based polymer A and 0.003 part of carbon dioxide-based polymer B;
s2: melting and blending the carbon dioxide-based polymer B and the modified polylactic acid by a double-screw extruder, extruding, granulating and drying to obtain a material a; melting and blending the carbon dioxide-based polymer A, polybutylene succinate, ethylene bis-stearamide and stearic acid amide by a double-screw extruder, extruding, granulating and drying to obtain a material b;
the raw materials comprise the following components in parts by weight: 3 parts of carbon dioxide-based polymer, 65 parts of modified polylactic acid, 30 parts of polybutylene succinate, 0.3 part of ethylene bis stearamide and 0.05 part of stearic acid amide; the carbon dioxide-based polymer is obtained by compounding 2.7 parts of carbon dioxide-based PPC and 0.3 part of carbon dioxide-based polyurethane, and the brand of the carbon dioxide-based PPC is PPC/Henan Yang Tianguan;
the preparation method of the carbon dioxide-based polyurethane comprises the following steps:
(1) Stirring 0.42mol of zinc sulfate, 300mL of deionized water and 150mL of tert-butyl alcohol at 40 ℃, dropwise adding 100mL of a 0.20mol/L potassium cobalt cyanide aqueous solution into the zinc sulfate solution through a constant-pressure dropping funnel within 40min, centrifuging the suspension at a centrifugal speed of 5500rpm for 2min after ultrasonic stirring, washing the separated slurry with a deionized water and tert-butyl alcohol mixed solution, centrifuging the suspension at a centrifugal speed of 5500rpm for 2min, continuously washing the separated slurry with the mixed solution, gradually increasing the proportion of tert-butyl alcohol to water in the mixed solution until pure tert-butyl alcohol is used as a washing agent, centrifuging the solid, and drying at 40 ℃ in vacuum to obtain the zinc-cobalt-based double metal cyanide;
(2) Adding 35g of zinc-cobalt-based double metal cyanide, 77kg of cyclopentane epoxide and 3kg of isophthalic acid into a reaction kettle, then introducing carbon dioxide gas, introducing the carbon dioxide gas under the pressure of 2MPa, heating to 75 ℃ for reaction for 7 hours, cooling the reaction kettle to 20 ℃ after the reaction is finished, releasing the gas in the kettle, dissolving the gas in deionized water, filtering the product, and removing the zinc-cobalt-based double metal cyanide to obtain carbon dioxide-based polyol;
(3) 50g of carbon dioxide-based polyol is dehydrated for 2h under reduced pressure in an oil bath at the temperature of 80 ℃, 22g of isophorone diisocyanate and 1.8g of 1,4 butanediol are added to be mixed and stirred under the atmosphere of nitrogen, then 0.8g of 3-methylamino-1,2-propanediol, 1g of dibutyltin dilaurate and 0.05g of 2-butanone are added to be mixed and stirred, then 0.5g of triethylamine is used for neutralization for 30min at the temperature of 30 ℃, and carbon dioxide-based polyurethane is obtained by reduced pressure distillation in a water bath at the temperature of 40 ℃;
the preparation method of the modified polylactic acid comprises the following steps: heating 25mmol of polybutyrolactam and 19.7g of formic acid to 60 ℃ to obtain a formic acid solution of polybutyrolactam, mixing 2mmol of trioxymethylene and 70mmol of formic acid to obtain a trioxymethylene mixed solution, adding the trioxymethylene mixed solution into the prepared formic acid solution of polybutyrolactam, heating to 60 ℃ to react for 1 hour, precipitating by using acetone, and performing suction filtration for 3 times to obtain hydroxylated polybutyrolactam after vacuum drying; 50g of hydroxylated polybutyrolactam and 400g of polylactic acid are blended and extruded to obtain modified polylactic acid;
s3: and (3) performing micro-nano co-extrusion on the material a and the material b, cooling to 18 ℃, and then drawing a pipe by using a pipe drawing machine to obtain the fully biodegradable straw.
Example 5
A preparation method of a full-biodegradation straw comprises the following steps:
s1: dividing the carbon dioxide-based polymer into 2 parts according to the weight part ratio of 99 to 1, wherein the carbon dioxide-based polymer A is 0.594 part, and the carbon dioxide-based polymer B is 0.006 part;
s2: melting and blending the carbon dioxide-based polymer B and the modified polylactic acid by a double-screw extruder, extruding, granulating and drying to obtain a material a; melting and blending the carbon dioxide-based polymer A, polybutylene succinate, ethylene bis-stearamide and stearic acid amide by a double-screw extruder, extruding, granulating and drying to obtain a material b;
the straw comprises the following components in parts by weight: 6 parts of carbon dioxide-based polymer, 60 parts of polylactic acid, 32 parts of polybutylene succinate, 0.4 part of ethylene bis stearamide and 0.1 part of stearic acid amide; the carbon dioxide-based polymer is obtained by compounding 5.4 parts of carbon dioxide-based PPC and 0.6 part of carbon dioxide-based polyurethane, and the brand of the carbon dioxide-based PPC is PPC/Henan Yang Tianguan;
the preparation method of the carbon dioxide-based polyurethane comprises the following steps:
(1) Stirring 0.42mol of zinc sulfate, 300mL of deionized water and 150mL of tert-butyl alcohol at 40 ℃, dropwise adding 100mL of a 0.20mol/L potassium cobalt cyanide aqueous solution into the zinc sulfate solution through a constant-pressure dropping funnel within 40min, centrifuging the suspension at a centrifugal speed of 5500rpm for 2min after ultrasonic stirring, washing the separated slurry with a deionized water and tert-butyl alcohol mixed solution, centrifuging the suspension at a centrifugal speed of 5500rpm for 2min, continuously washing the separated slurry with the mixed solution, gradually increasing the proportion of tert-butyl alcohol to water in the mixed solution until pure tert-butyl alcohol is used as a washing agent, centrifuging the solid, and drying at 40 ℃ in vacuum to obtain the zinc-cobalt-based double metal cyanide;
(2) Adding 35g of zinc-cobalt-based double metal cyanide, 77kg of cyclopentane epoxide and 3kg of isophthalic acid into a reaction kettle, then introducing carbon dioxide gas, introducing the carbon dioxide gas under the pressure of 2.1MPa, heating to 75 ℃ for reaction for 7 hours, cooling the reaction kettle to 22 ℃ after the reaction is finished, releasing the gas in the kettle, dissolving the gas in deionized water, filtering the product, and removing the zinc-cobalt-based double metal cyanide to obtain carbon dioxide-based polyol;
(3) 50g of carbon dioxide-based polyol is dehydrated for 2 hours under reduced pressure in an oil bath at the temperature of 80 ℃, 22g of isophorone diisocyanate and 5g of 1,4 butanediol are added to be mixed and stirred under the atmosphere of nitrogen, then 6g of 3-methylamino-1,2-propanediol, 1g of dibutyltin dilaurate and 0.05g of 2-butanone are added to be mixed and stirred, then 0.5g of triethylamine is used for neutralization for 30 minutes at the temperature of 30 ℃, and carbon dioxide-based polyurethane is obtained through reduced pressure distillation in a water bath at the temperature of 40 ℃;
the preparation method of the modified polylactic acid comprises the following steps: heating 25mmol of polybutyrolactam and 19.7g of formic acid to 60 ℃ to obtain a formic acid solution of the polybutyrolactam, mixing 2.5mmol of trioxymethylene and 70mmol of formic acid to obtain a trioxymethylene mixed solution, adding the trioxymethylene mixed solution into the prepared formic acid solution of the polybutyrolactam, heating to 60 ℃ to react for 1h, precipitating by using acetone, and carrying out suction filtration for 4 times of vacuum drying to obtain hydroxylated polybutyrolactam; 50g of hydroxylated polybutyrolactam and 400g of polylactic acid are blended and extruded to obtain modified polylactic acid;
s3: and (3) performing micro-nano co-extrusion on the material a and the material b, cooling to 20 ℃, and then drawing a pipe by using a pipe drawing machine to obtain the fully biodegradable straw.
Example 6
A preparation method of a full-biodegradation straw comprises the following steps:
s1: dividing the carbon dioxide-based polymer into 2 parts according to the weight part ratio of 99 to 1, wherein the weight parts are 0.792 part of the carbon dioxide-based polymer A and 0.008 part of the carbon dioxide-based polymer B;
s2: melting and blending the carbon dioxide-based polymer B and the modified polylactic acid by a double-screw extruder, extruding, granulating and drying to obtain a material a; melting and blending the carbon dioxide-based polymer A, polybutylene succinate, ethylene bis-stearamide and stearic acid amide by a double-screw extruder, extruding, granulating and drying to obtain a material b;
the straw comprises the following components in parts by weight: 8 parts of carbon dioxide-based polymer, 50 parts of polylactic acid, 40 parts of polybutylene succinate, 0.5 part of ethylene bis stearamide and 0.3 part of stearic acid amide; the carbon dioxide-based polymer is obtained by compounding 7.2 parts of carbon dioxide-based PPC and 0.8 part of carbon dioxide-based polyurethane, and the brand of the carbon dioxide-based PPC is PPC/Henan Yang Tianguan;
the preparation method of the carbon dioxide-based polyurethane comprises the following steps:
(1) Stirring 0.42mol of zinc sulfate, 300mL of deionized water and 150mL of tert-butyl alcohol at 40 ℃, dropwise adding 100mL of a 0.20mol/L potassium cobalt cyanide aqueous solution into the zinc sulfate solution through a constant-pressure dropping funnel within 40min, centrifuging the suspension at a centrifugal speed of 5500rpm for 2min after ultrasonic stirring, washing the separated slurry with a deionized water and tert-butyl alcohol mixed solution, centrifuging the suspension at a centrifugal speed of 5500rpm for 2min, continuously washing the separated slurry with the mixed solution, gradually increasing the proportion of tert-butyl alcohol to water in the mixed solution until pure tert-butyl alcohol is used as a washing agent, centrifuging the solid, and drying at 40 ℃ in vacuum to obtain the zinc-cobalt-based double metal cyanide;
(2) Adding 35g of zinc-cobalt-based double metal cyanide, 77kg of cyclopentane epoxide and 3kg of isophthalic acid into a reaction kettle, then introducing carbon dioxide gas, introducing the carbon dioxide gas under the pressure of 2.2MPa, heating to 75 ℃ for reaction for 7 hours, cooling the reaction kettle to 25 ℃ after the reaction is finished, releasing the gas in the kettle, dissolving the gas in deionized water, filtering the product, and removing the zinc-cobalt-based double metal cyanide to obtain carbon dioxide-based polyol;
(3) 50g of carbon dioxide-based polyol is dehydrated for 2h under reduced pressure in an oil bath at the temperature of 80 ℃, 22g of isophorone diisocyanate and 6.3g of 1,4 butanediol are added to be mixed and stirred under the atmosphere of nitrogen, then 6.6g of 3-methylamino-1,2-propanediol, 1g of dibutyltin dilaurate and 0.05g of 2-butanone are added to be mixed and stirred, then 0.5g of triethylamine is used for neutralization for 30min at the temperature of 30 ℃, and carbon dioxide-based polyurethane is obtained by reduced pressure distillation in a water bath at the temperature of 40 ℃;
the preparation method of the modified polylactic acid comprises the following steps: heating 25mmol of polybutyrolactam and 19.7g of formic acid to 60 ℃ to obtain a formic acid solution of the polybutyrolactam, mixing 3mmol of trioxymethylene and 70mmol of formic acid to obtain a trioxymethylene mixed solution, then adding the trioxymethylene mixed solution into the prepared formic acid solution of the polybutyrolactam, heating to 60 ℃ to react for 1h, precipitating by using acetone, and carrying out suction filtration for 5 times of vacuum drying to obtain hydroxylated polybutyrolactam; 50g of hydroxylated polybutyrolactam and 400g of polylactic acid are blended and extruded to obtain modified polylactic acid;
s3: and (3) performing micro-nano co-extrusion on the material a and the material b, cooling to 25 ℃, and then drawing a pipe by using a pipe drawing machine to obtain the fully biodegradable straw.
The micro-nano co-extrusion mentioned in examples 4 to 6 was performed by a micro-nano co-extrusion device consisting of a twin-screw extruder, a connector, a distributor, a layer multiplier I, a layer multiplier II, and an extrusion die;
the temperature from the cylinder zone of the double-screw extruder to the extrusion die is 175 ℃, 185 ℃, 195 ℃ and 185 ℃ in sequence;
the melt obtained by plasticizing and melting materials a and b through a double-screw extruder and the double-screw extruder is subjected to connector and distributor to obtain 4 layers of melt which are alternately distributed, the 4 layers of melt enter a layer multiplier I and are divided into 4 strands of melt, the 4 strands of melt are gradually changed into vertical arrangement from horizontal arrangement in a runner, then confluence is carried out to obtain 16 layers of melt, the 16 layers of melt are subjected to layer multiplier II to obtain 64 layers of melt, and finally, the melt passes through an extrusion die to obtain the full-biodegradation straw.
Comparative example 1
Example 5 was used as a control, the carbon dioxide-based polymer was carbon dioxide-based PPC, the carbon dioxide-based PPC brand was PPC/south-Henan-Yang Tianguan, and the other procedures were normal.
Comparative example 2
With example 5 as a control, the polybutyrolactam was not hydroxylated during the preparation of the modified polylactic acid, and the polybutyrolactam was added directly, and the other steps were normal.
Comparative example 3
With example 5 as a control, the modified polylactic acid was replaced with polylactic acid, and the other steps were normal.
Comparative example 4
Taking the example 5 as a control group, the carbon dioxide-based polymer is not divided into 2 parts according to the weight part ratio of 99 during micro-nano co-extrusion, and other procedures are normal.
And (3) performance testing: the performance of the straws prepared in the examples 1 to 6 and the comparative examples 1 to 4 is tested, and the straws prepared in the above are tested according to the biological decomposition rate of 45d in the test GB/T19277.1-20113; testing the tensile strength and the elongation at break by referring to GB/T1040.1-2018; the heat distortion temperature is tested by referring to ASTM D1525; specific data are shown in table 1;
TABLE 1
Examples 1 to 6 are degradation straws prepared according to the present invention, and it can be seen from the comparison of example 5 with example 2 and comparative example 2 that the heat resistance of the straw is greatly improved by modifying polylactic acid with hydroxylated polybutyrolactam and matching with the corresponding process design;
comparing the example 5 with the comparative example 1, it can be seen that the carbon dioxide-based polyurethane is prepared by using the aqueous cationic polyurethane, the carbon dioxide-based polyol synthesized based on the telomerization reaction of carbon dioxide and cyclopentane epoxide has a structure of coexisting carbonate and ether, and the carbon dioxide-based polyol is refined under the catalysis of zinc-cobalt-based double metal cyanide; 3-methylamino-1,2 is prepared by changing tertiary amine on the upper end group of a polyurethane chain and using carbon dioxide-based polyalcohol, and the propylene glycol-terminated water-based cationic polyurethane can be used for obtaining a degradation straw with excellent mechanical property and heat resistance under the condition of reducing the using amount of a hydrophilic chain extender; comparing example 5 with comparative examples 1 and 3, it can be seen that the hydroxylated polybutyrolactam is used to modify polylactic acid and prepare 3-methylamino-1,2, and the propylene glycol end-capped carbon dioxide-based polyurethane synergistically improves the heat-resistant stability of the straw;
compared with the comparative example 4, the embodiment 5 shows that the carbon dioxide-based polymer is not divided into 2 parts according to the weight part ratio of 99 in the micro-nano co-extrusion, and the carbon dioxide-based polymer is directly blended, so that the thermal stability is reduced by 10.8%, and the mechanical strength is also reduced, therefore, when the micro-nano co-extrusion is performed, the carbon dioxide-based polymer is divided into 2 parts according to the weight part ratio of 99, and 1% of the carbon dioxide-based polymer is taken as a compatibilizer of modified polylactic acid, so that the mechanical strength and the heat resistance stability of the straw can be greatly improved.
In conclusion, the straw prepared by the invention has excellent mechanical property and chemical property, and meanwhile, has excellent temperature resistance and good application prospect.
The above description is only an example of the present invention, and is not intended to limit the scope of the present invention, and all modifications and equivalents of the present invention, which are made by the present specification and directly/indirectly applied to other related technical fields, are included in the scope of the present invention.
Claims (7)
1. The preparation method of the full-biodegradable straw is characterized by comprising the following steps of: mixing the raw materials, adding the mixture into a double-screw extruder with a cylinder temperature of 160-180 ℃ and a die head temperature of 170 ℃, blending, extruding and granulating, cooling to 18-25 ℃, drawing a pipe by using a pipe drawing machine, and then carrying out heat treatment at 105 ℃ for 5min to obtain a full-biodegradable straw;
the raw materials comprise the following components in parts by weight: 3-8 parts of carbon dioxide-based polymer, 52-65 parts of modified polylactic acid, 30-40 parts of polybutylene succinate, 0.3-0.5 part of ethylene bis stearamide, 0.680-0.3 part of compatibilizer and 0.05-0.3 part of stearic acid amide;
the carbon dioxide-based polymer is obtained by compounding carbon dioxide-based polyurethane and carbon dioxide-based PPC according to the weight part ratio of 1:9;
the preparation method of the carbon dioxide-based polyurethane comprises the following steps:
(1) Stirring zinc sulfate, deionized water and tert-butyl alcohol at 40 ℃ to obtain a zinc sulfate solution, dropwise adding a potassium cobalt cyanide aqueous solution into the zinc sulfate solution, ultrasonically stirring, centrifuging the suspension for 2min at a centrifugal speed of 5500rpm, washing the separated slurry with a mixed solution of the deionized water and the tert-butyl alcohol, centrifuging the suspension for 2min at a centrifugal speed of 5500rpm, continuously washing the separated slurry with the mixed solution of the deionized water and the tert-butyl alcohol, gradually increasing the proportion of the tert-butyl alcohol to the water in the mixed solution until pure tert-butyl alcohol is used as a detergent, centrifuging the solid, and drying the solid at 40 ℃ in vacuum to obtain the zinc-cobalt-based double metal cyanide;
(2) Adding zinc-cobalt-based double metal cyanide, cyclopentane epoxide and isophthalic acid into a reaction kettle, then introducing carbon dioxide gas, heating to 75 ℃ for reaction for 7 hours, cooling the reaction kettle to 20-25 ℃ after the reaction is finished, releasing the gas in the reaction kettle, dissolving the product in deionized water, and filtering to obtain carbon dioxide-based polyol;
(3) Dehydrating carbon dioxide-based polyol in an oil bath at 80 ℃ under reduced pressure for 2h, adding isophorone diisocyanate and 1,4 butanediol to mix and stir in the nitrogen atmosphere, then adding 3-methylamino-1,2-propanediol, dibutyltin dilaurate and 2-butanone to mix and stir, then neutralizing with triethylamine at 30 ℃ for 30min, and obtaining carbon dioxide-based polyurethane through reduced pressure distillation in a water bath at 40 ℃;
the preparation method of the modified polylactic acid comprises the following steps: heating polybutyrolactam and formic acid to 60 ℃ to obtain a formic acid solution of the polybutyrolactam, mixing trioxymethylene and the formic acid to obtain a trioxymethylene mixed solution, then adding the trioxymethylene mixed solution into the formic acid solution of the polybutyrolactam, heating to 60 ℃, preserving heat for 1h, precipitating by using acetone, carrying out suction filtration for 3-5 times, and then carrying out vacuum drying to obtain hydroxylated polybutyrolactam; and (3) blending and extruding the hydroxylated polybutyrolactam and the polylactic acid to obtain the modified polylactic acid.
2. The method for preparing a full biodegradable straw as claimed in claim 1, wherein the pressure of the carbon dioxide gas is 2-2.2MPa.
3. The method for preparing the full-biodegradation straw according to claim 1, wherein the volume ratio of the deionized water to the tertiary butanol in the zinc sulfate solution is 2:1; the mass ratio of the carbon dioxide-based polyol to the isophorone diisocyanate to the 1,4 butanediol to the 3-methylamino-1,2-propanediol is (1.8-6.3) to (0.8-6.6) of 50.
4. The method for preparing a full biodegradation straw according to claim 1, wherein the molar ratio of said polybutyrolactam to said formic acid in said solution of polybutyrolactam is 5; in the trioxymethylene mixed solution, the molar ratio of trioxymethylene to formic acid is (2-3) to 70; the mass ratio of the hydroxylated polybutyrolactam to the polylactic acid is 1:8.
5. The method for preparing the full-biodegradation straw according to claim 1, wherein the method comprises the following steps:
s1: dividing the carbon dioxide-based polymer into 2 parts according to the weight part ratio of 99;
s2: melting and blending the carbon dioxide-based polymer B and the modified polylactic acid by a double-screw extruder, extruding, granulating and drying to obtain a material a; melting and blending the carbon dioxide-based polymer A, polybutylene succinate, ethylene bis-stearamide and stearic acid amide by a double-screw extruder, extruding, granulating and drying to obtain a material b;
s3: and (3) granulating the material a and the material b by micro-nano co-extrusion, cooling to 18-25 ℃, and drawing a pipe by using a pipe drawing machine to obtain the fully biodegradable straw.
6. The method for preparing a full-biodegradable straw as claimed in claim 5, wherein the temperature from the barrel zone of the twin-screw extruder to the extrusion die is 175 ℃, 185 ℃, 195 ℃ and 185 ℃ in sequence.
7. A fully biodegradable straw, characterized in that it is prepared by the method of any one of claims 1 to 6.
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