CN114031909A - Starch-based degradable desorption tube material and preparation method thereof - Google Patents
Starch-based degradable desorption tube material and preparation method thereof Download PDFInfo
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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
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D23/00—Producing tubular articles
- B29D23/001—Pipes; Pipe joints
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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
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- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C08L2203/18—Applications used for pipes
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Abstract
The invention discloses a starch-based degradable straw material and a preparation method thereof, belonging to the technical field of high polymer materials, wherein the starch-based degradable straw material comprises the following components in parts by weight: 60-80 parts of PLA, 3-7 parts of PBAT, 5-30 parts of starch, 3-10 parts of plasticizer, 0.5-1 part of nucleating agent, 0.5-1 part of erucamide and 0.5-2 parts of hyperbranched assistant; the preparation method of the starch-based degradable desorption tube material comprises the following steps: PLA, PBAT, starch, a plasticizer, a nucleating agent, erucamide and hyperbranched resin are melted and blended uniformly at a high speed and then are extruded to obtain a starch-based degradable straw material; the starch-based degradable desorption tube material has high heat resistance, high toughness and biodegradability.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a starch-based degradable desorption tube material and a preparation method thereof.
Background
Biodegradable plastics, also called biodegradable plastics, are those which are degraded by the action of microorganisms present in nature under conditions of nature such as soil and/or sandy soil, and/or under specific conditions such as composting conditions or anaerobic digestion conditions or in aqueous culture solutions, and finally completely degraded to carbon dioxide (CO)2) Or/and methane (CH)4) Water (H)2O) and mineralized inorganic salts of the elements contained therein, and new plastics of biomass. Polylactic acid (PLA) is a completely biodegradable polymer, has mechanical properties similar to that of PET, can replace PET in a plurality of application fields, such as making cups, lunch boxes, lids and the like, and knife, fork, spoons, straws and the like used in the market at present are mostly made of PP materials, and the PP materials belong to petrochemical-based materials, are not degradable, and can cause environmental pollution when being discarded in the environment after being used. PLA belongs to a completely degradable material, can be completely degraded into carbon dioxide and water in the environment with the temperature of 50 ℃ and the humidity of 50 percent within 3 to 6 months, enters the environment, and has no pollution to the environment. Thus, polylactic acid is considered to be suitable for use in place of PP for extrusion of straws. The suction pipe and the knife and fork spoon which are suitable for being made of polylactic acid can only be used in the field of cold drinks at 30-50 ℃ and cannot be used at 80-100 ℃, in addition, the price of the polylactic acid is 3 ten thousand per ton, and the material cost is high, so that the application range of the polylactic acid as the suction pipe and other tableware is limited, and the polylactic acid as the tableware has the defect of poor heat resistance, and has the characteristic of being relatively brittle and has the problems of brittleness, breakage and cracking in the use process. With the vigorous promotion of national plastic prohibited orders, the tableware will be fully used in the futureThe polylactic acid composite material is made of degradable materials, so that the development of the polylactic acid composite material with high temperature resistance and high toughness is imminent.
In the prior art, the heat resistance and toughening modification of polylactic acid are carried out, and the high-purity polylactic acid is prepared by controlling the polymerization process and the purity of monomers such as multiple separation and purification in the aspect of polymerization. For example, the patent "CN 100567246C" is a process for preparing high-purity L-lactic acid, which adopts the idea. In another method, a nucleating agent is added in the polymerization process of polylactic acid to improve the heat resistance of the polylactic acid by increasing the crystallization rate, for example, patent "CN 101475736B" discloses an injection molding method of polylactic acid, which comprises mixing the nucleating agent into a solvent, mixing the polylactic acid into the solvent, drying the polylactic acid by a drying device to perform low-degree crystallization, and improving the heat resistance of the polylactic acid by matching with an injection molding process. The method has complex process, is not environment-friendly and is not beneficial to large-scale production. Patent "CN 106589872B" discloses a high-strength heat-resistant polylactic acid composition, which mainly adopts inorganic filler and glass fiber to improve heat resistance, and elastomer with core-shell structure to improve toughness. But the inorganic substance and the glass fiber are added, so that the flowability of the polylactic acid can be greatly reduced, a mold is difficult to fill with a melt in the injection molding process, and the stable injection molding cannot be realized, and the problems of uneven mixing, material mixing and powder leakage in the processing process are caused by the addition of the inorganic filler. On the other hand, the core is added with an elastomer with a core-shell structure, and the core layer is polybutadiene or polyisoprene; the shell layer is composed of styrene and poly D-lactic acid, polybutadiene or polyisoprene is a non-degradable material, degradation of the polylactic acid is influenced by introduction, the elastomer with the core-shell structure is expensive, the toughening effect is difficult to achieve after 5% of the elastomer is added, the degradable national standard GBT 20197-.
In order to improve the heat resistance of polylactic acid, increase the toughness of the polylactic acid, reduce the material cost, overcome the defects of low heat resistance, large material brittleness, high cost and the like, a starch-based degradable straw material with heat resistance, toughness and low cost and a preparation method thereof are developed, the straw material can be degraded into carbon dioxide and water in 3-6 months under the condition of compost, and the relative biological decomposition rate is more than 90 percent.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention aims to solve the technical problem of providing a starch-based degradable desorption tube material and a preparation method thereof.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
the starch-based degradable desorption tube material comprises the following components in parts by weight:
60-80 parts of PLA, 3-7 parts of PBAT, 5-30 parts of starch, 3-10 parts of plasticizer, 0.5-1 part of nucleating agent, 0.5-1 part of erucamide and 0.5-2 parts of hyperbranched assistant;
wherein the optical purity of the PLA is 95-100%, and the melt index (190 ℃, 2.16kg) of the PLA is 2-8g/10 min.
As a further scheme of the invention: the paint comprises the following components in parts by weight:
65-70 parts of PLA, 3-7 parts of PBAT, 5-30 parts of starch, 3-10 parts of plasticizer, 0.5-1 part of nucleating agent, 0.5-1 part of erucamide and 0.5-2 parts of hyperbranched assistant;
wherein the optical purity of the PLA is more than or equal to 99.9 percent, and the melt index (190 ℃, 2.16kg) of the PLA is 3-7g/10 min.
As a further scheme of the invention: the melt index of the PBAT is 3 to 6g/10min (190 ℃, 2.16 kg).
As a further scheme of the invention: the starch is one or a mixture of two of corn starch and cassava starch, the mesh number of the starch is more than or equal to 100 meshes, and the whiteness is more than or equal to 90%.
As a further scheme of the invention: the plasticizer is one or a mixture of glycerol triacetate and tributyl citrate.
As a further scheme of the invention: the nucleating agent is one or a mixture of more of potassium benzene sulfonate, zinc phenyl phosphate, dibenzoyl sebacate, organic phosphate and cyclodextrin.
As a further scheme of the invention: the nucleating agent is a blend of sebacic acid dibenzoyl hydrazine and cyclodextrin, the erucamide is selected from one of PMC model of ArmoslipE, British Poa (Croda) and Korean pathwel, the hyperbranched auxiliary agent is solid powder, and the melting range is 145-155 ℃.
The preparation method of the starch-based degradable desorption tube material comprises the following steps:
grinding the nucleating agent particles in a mortar to obtain uniformly dispersed nucleating agent powder A;
mixing the powder A, the starch, the erucamide and the hyperbranched auxiliary agent in a cold mixer to obtain uniformly mixed powder B;
adding PLA and PBAT into a high-speed mixer, blending for 20min, uniformly adding a plasticizer while stirring in the process of blending the mixture, and blending for 10min to obtain a mixture C;
adding the powder B and the powder C into a high-speed mixer, and mixing for 10min to obtain a blend D;
adding the blend D into a double-screw extruder for melt extrusion granulation to obtain starch-based degradable straw material particles E;
and adding the degradable particles E into a single-screw straw, extruding and pulling the straw to obtain the starch-based degradable straw.
As a further scheme of the invention: the temperature of the granulation and tube drawing is 160-205 ℃.
As a further scheme of the invention: the conditions for granulating and extruding the drawn tube comprise: the temperature of the first zone is 170 +/-5 ℃, the temperature of the second zone is 180 +/-5 ℃, the temperature of the third zone is 190 +/-5 ℃, the temperature of the fourth zone is 195 +/-5 ℃ and the temperature of the fifth zone is 200 +/-5 ℃.
Compared with the prior art, the invention has the beneficial effects that: the invention provides a starch-based degradable desorption tube material and a preparation method thereof, wherein sebacic acid dibenzoylhydrazine and cyclodextrin in a nucleating agent are compounded with PLA, the compatibility with PLA is good, and the crystallization rate of PLA is accelerated in a lower addition range, so that the heat resistance is improved; the glycerol triacetate and the tributyl citrate in the plasticizer are blended with the PBAT for use and compounded with the PLA, so that the brittleness of the PLA can be reduced, and the toughness of the PLA can be improved; the invention adopts starch as filling material to be compounded with PLA, thereby greatly reducing the material cost while ensuring the biodegradability; the invention adopts a blending granulation mode, and the nucleating agent is ground into powder for use, thereby being beneficial to improving the dispersity and crystallization efficiency of the nucleating agent in the composite material; the preparation method is characterized in that the sebacic acid dibenzoyl hydrazine, the cyclodextrin, the glycerol triacetate, the PBAT, the erucamide and the PLA are blended and granulated, the process is simple, the operation condition is mild, and the preparation method is suitable for industrial large-scale production.
Detailed Description
Example 1
The preparation method of the starch-based degradable desorption tube material comprises the following steps:
(1) grinding 0.15 part of sebacic acid dibenzoylhydrazine and 0.25 part of cyclodextrin particles in a mortar for 15min to obtain uniformly dispersed nucleating agent powder A;
(2) 0.4 part of powder A, 28.3 parts of 100-mesh corn starch, 0.6 part of erucamide and 0.4 part of hyperbranched auxiliary agent are mixed for 5min at low speed in a cold mixer to obtain uniformly mixed powder B;
(3) adding 64 parts of PLA and 0.35 part of PBAT into high-speed mixing, carrying out high-speed blending for 20min, uniformly adding 7.5 parts of tributyl citrate while stirring in the process of blending the mixture, and carrying out high-speed blending for 10min to obtain a mixture C;
(4) adding the powder B and the mixture C into a high-speed mixer, and mixing at a high speed for 10min to obtain a blend D;
(5) melting, extruding and granulating the blend D to obtain the starch-based degradable granular material E; the melt extrusion conditions include: the temperature of the first zone is 170 ℃, the temperature of the second zone is 180 ℃, the temperature of the third zone is 190 ℃, the temperature of the fourth zone is 195 ℃ and the temperature of the fifth zone is 200 ℃; the rotating speed of the screw is 200-350 rpm/min;
(6) adding the degradable particles E into a single-screw straw extruder to extrude and draw a pipe to obtain a starch-based degradable straw, wherein the conditions of extruding and drawing the pipe comprise: the temperature in the first zone is 170 ℃, the temperature in the second zone is 180 ℃, the temperature in the third zone is 190 ℃, the temperature in the fourth zone is 195 ℃ and the temperature in the fifth zone is 200 ℃.
Example 2
The preparation method of the starch-based degradable desorption tube material comprises the following steps:
(1) grinding 0.15 part of sebacic acid dibenzoylhydrazine and 0.25 part of cyclodextrin particles in a mortar for 15min to obtain uniformly dispersed nucleating agent powder A;
(2) 0.4 part of powder A, 28.3 parts of 100-mesh corn starch, 0.6 part of erucamide and 0.4 part of hyperbranched auxiliary agent are mixed for 5min at low speed in a cold mixer to obtain uniformly mixed powder B;
(3) adding 64 parts of PLA into the high-speed mixing, carrying out high-speed blending for 5min, uniformly adding 7.85 parts of PBAT while stirring in the process of blending the mixture, and carrying out high-speed blending for 10min to obtain a mixture C;
(4) adding the powder B and the mixture C into a high-speed mixer, and mixing at a high speed for 10min to obtain a blend D;
(5) melting, extruding and granulating the blend D to obtain the starch-based degradable granular material E; the melt extrusion conditions include: the temperature of the first zone is 170 ℃, the temperature of the second zone is 180 ℃, the temperature of the third zone is 190 ℃, the temperature of the fourth zone is 195 ℃ and the temperature of the fifth zone is 200 ℃; the rotating speed of the screw is 200-350 rpm/min;
(6) adding the degradable particles E into a single-screw straw extruder to extrude and draw a pipe to obtain a starch-based degradable straw, wherein the conditions of extruding and drawing the pipe comprise: the temperature in the first zone is 170 ℃, the temperature in the second zone is 180 ℃, the temperature in the third zone is 190 ℃, the temperature in the fourth zone is 195 ℃ and the temperature in the fifth zone is 200 ℃.
Example 3
The preparation method of the starch-based degradable desorption tube material comprises the following steps:
(1) grinding 0.15 part of sebacic acid dibenzoylhydrazine and 0.25 part of cyclodextrin particles in a mortar for 15min to obtain uniformly dispersed nucleating agent powder A;
(2) 0.4 part of powder A, 28.3 parts of cassava starch with 100 meshes, 0.6 part of erucamide and 0.5 part of hyperbranched auxiliary agent are mixed for 5min at low speed in a cold mixer to obtain uniformly mixed powder B;
(3) adding 64 parts of PLA and 0.35 part of PBAT into high-speed mixing, blending at a high speed for 20min, uniformly adding 7.5 parts of glycerol triacetate while stirring in the process of blending the mixture, and blending at a high speed for 10min to obtain a mixture C;
(4) adding the powder B and the mixture C into a high-speed mixer, and mixing at a high speed for 10min to obtain a blend D;
(5) melting, extruding and granulating the blend D to obtain the starch-based degradable granular material E; the melt extrusion conditions include: the temperature of the first zone is 170 ℃, the temperature of the second zone is 180 ℃, the temperature of the third zone is 190 ℃, the temperature of the fourth zone is 195 ℃ and the temperature of the fifth zone is 200 ℃; the rotating speed of the screw is 200-350 rpm/min;
(6) adding the degradable particles E into a single-screw straw extruder to extrude and draw a pipe to obtain a starch-based degradable straw, wherein the conditions of extruding and drawing the pipe comprise: the temperature in the first zone is 170 ℃, the temperature in the second zone is 180 ℃, the temperature in the third zone is 190 ℃, the temperature in the fourth zone is 195 ℃ and the temperature in the fifth zone is 200 ℃.
Example 4
The preparation method of the starch-based degradable desorption tube material comprises the following steps:
(1) grinding 0.15 part of sebacic acid dibenzoylhydrazine and 0.25 part of cyclodextrin particles in a mortar for 15min to obtain uniformly dispersed nucleating agent powder A;
(2) 0.4 part of powder A, 28.3 parts of 100-mesh corn starch, 0.6 part of erucamide and 0.5 part of hyperbranched auxiliary agent are mixed for 5min at low speed in a cold mixer to obtain uniformly mixed powder B;
(3) adding 64 parts of PLA into high-speed mixing, carrying out high-speed blending for 5min, uniformly adding 5.35 parts of PBAT and 2 parts of glycerol triacetate while stirring in the process of blending the mixture, and carrying out high-speed blending for 10min to obtain a mixture C;
(4) adding the powder B and the mixture C into a high-speed mixer, and mixing at a high speed for 10min to obtain a blend D;
(5) melting, extruding and granulating the blend D to obtain the starch-based degradable granular material E; the melt extrusion conditions include: the temperature of the first zone is 170 ℃, the temperature of the second zone is 180 ℃, the temperature of the third zone is 190 ℃, the temperature of the fourth zone is 195 ℃ and the temperature of the fifth zone is 200 ℃; the rotating speed of the screw is 200-350 rpm/min;
(6) adding the degradable particles E into a single-screw straw extruder to extrude and draw a pipe to obtain a starch-based degradable straw, wherein the conditions of extruding and drawing the pipe comprise: the temperature in the first zone is 170 ℃, the temperature in the second zone is 180 ℃, the temperature in the third zone is 190 ℃, the temperature in the fourth zone is 195 ℃ and the temperature in the fifth zone is 200 ℃.
Example 5
The preparation method of the starch-based degradable desorption tube material comprises the following steps:
(1) grinding 0.15 part of sebacic acid dibenzoylhydrazine and 0.25 part of cyclodextrin particles in a mortar for 15min to obtain uniformly dispersed nucleating agent powder A;
(2) 0.4 part of powder A, 28.3 parts of 100-mesh corn starch, 0.6 part of erucamide and 0.5 part of hyperbranched auxiliary agent are mixed for 5min at low speed in a cold mixer to obtain uniformly mixed powder B;
(3) adding 64 parts of PLA into high-speed mixing, carrying out high-speed blending for 5min, uniformly adding 4.35 parts of PBAT and 3 parts of glycerol triacetate while stirring in the process of blending the mixture, and carrying out high-speed blending for 10min to obtain a mixture C;
(4) adding the powder B and the mixture C into a high-speed mixer, and mixing at a high speed for 10min to obtain a blend D;
(5) melt-extruding and granulating the blend D to obtain the starch-based degradable granular material E; the melt extrusion conditions include: the temperature of the first zone is 170 ℃, the temperature of the second zone is 180 ℃, the temperature of the third zone is 190 ℃, the temperature of the fourth zone is 195 ℃ and the temperature of the fifth zone is 200 ℃; the rotating speed of the screw is 200-350 rpm/min;
(6) adding the degradable particles E into a single-screw straw extruder to extrude and draw a pipe to obtain a starch-based degradable straw, wherein the conditions of extruding and drawing the pipe comprise: the temperature in the first zone is 170 ℃, the temperature in the second zone is 180 ℃, the temperature in the third zone is 190 ℃, the temperature in the fourth zone is 195 ℃ and the temperature in the fifth zone is 200 ℃.
Comparative example 1
The preparation method of the starch-based degradable desorption tube material comprises the following steps:
(1) mixing 0.15 part of sebacic acid dibenzoylhydrazine and 0.25 part of cyclodextrin particles for 5min to obtain uniformly dispersed nucleating agent powder A;
(2) 0.4 part of powder A, 28.3 parts of 100-mesh corn starch, 0.6 part of erucamide and 0.5 part of hyperbranched auxiliary agent are mixed for 5min at low speed in a cold mixer to obtain uniformly mixed powder B;
(3) adding 64 parts of PLA and 0.35 part of PBAT into high-speed mixing, carrying out high-speed blending for 20min, uniformly adding 4 parts of PBAT and 3 parts of glycerol triacetate while stirring in the process of blending the mixture, and carrying out high-speed blending for 10min to obtain a mixture C;
(4) adding the powder B and the mixture C into a high-speed mixer, and mixing at a high speed for 10min to obtain a blend D;
(5) melt-extruding and granulating the blend D to obtain the starch-based degradable granular material E; the melt extrusion conditions include: the temperature of the first zone is 170 ℃, the temperature of the second zone is 180 ℃, the temperature of the third zone is 190 ℃, the temperature of the fourth zone is 195 ℃ and the temperature of the fifth zone is 200 ℃; the rotating speed of the screw is 200-350 rpm/min;
(6) adding the degradable particles E into a single-screw straw extruder to extrude and draw a pipe to obtain a starch-based degradable straw, wherein the conditions of extruding and drawing the pipe comprise: the temperature in the first zone is 170 ℃, the temperature in the second zone is 180 ℃, the temperature in the third zone is 190 ℃, the temperature in the fourth zone is 195 ℃ and the temperature in the fifth zone is 200 ℃.
Comparative example 2
The preparation method of the starch-based degradable desorption tube material comprises the following steps:
(1) grinding 0.15 part of sebacic acid dibenzoylhydrazine and 0.25 part of cyclodextrin particles in a mortar for 15min to obtain uniformly dispersed nucleating agent powder A;
(2) 0.4 part of powder A, 28.3 parts of cassava starch with 100 meshes, 0.6 part of erucamide and 0.5 part of hyperbranched resin are mixed for 5min at low speed in a cold mixer to obtain uniformly mixed powder B;
(3) adding 71 parts of PLA and 0.35 part of PBAT into high-speed mixing, and carrying out high-speed mixing for 20min to obtain a mixture C;
(4) adding the powder B and the mixture C into a high-speed mixer, and mixing at a high speed for 10min to obtain a blend D;
(5) melting, extruding and granulating the blend D to obtain the starch-based degradable granular material E; the melt extrusion conditions include: the temperature of the first zone is 170 ℃, the temperature of the second zone is 180 ℃, the temperature of the third zone is 190 ℃, the temperature of the fourth zone is 195 ℃ and the temperature of the fifth zone is 200 ℃; the rotating speed of the screw is 200-350 rpm/min;
(6) adding the degradable particles E into a single-screw straw extruder to extrude and draw a pipe to obtain a starch-based degradable straw, wherein the conditions of extruding and drawing the pipe comprise: the temperature in the first zone is 170 ℃, the temperature in the second zone is 180 ℃, the temperature in the third zone is 190 ℃, the temperature in the fourth zone is 195 ℃ and the temperature in the fifth zone is 200 ℃.
Comparative example 3
The preparation method of the starch-based degradable desorption tube material comprises the following steps:
(1) grinding 0.4 part of sebacic acid dibenzoylhydrazine for 15min to obtain uniformly dispersed nucleating agent powder A;
(2) 0.4 part of powder A, 28.3 parts of 100-mesh corn starch, 0.6 part of erucamide and 0.5 part of hyperbranched auxiliary agent are mixed for 5min at low speed in a cold mixer to obtain uniformly mixed powder B;
(3) adding 64 parts of PLA and 0.35 part of PBAT homopolymer into high-speed mixing, carrying out high-speed mixing for 20min, uniformly adding 4 parts of PBAT and 3 parts of glycerol triacetate while stirring in the process of mixing the mixture, and carrying out high-speed mixing for 10min to obtain a mixture C;
(4) adding the powder B and the mixture C into a high-speed mixer, and mixing at a high speed for 10min to obtain a blend D;
(5) melt-extruding and granulating the blend D to obtain the starch-based degradable granular material E; the melt extrusion conditions include: the temperature of the first zone is 170 ℃, the temperature of the second zone is 180 ℃, the temperature of the third zone is 190 ℃, the temperature of the fourth zone is 195 ℃ and the temperature of the fifth zone is 200 ℃; the rotating speed of the screw is 200-350 rpm/min;
(6) adding the degradable particles E into a single-screw straw extruder to extrude and draw a pipe to obtain a starch-based degradable straw, wherein the conditions of extruding and drawing the pipe comprise: the temperature in the first zone is 170 ℃, the temperature in the second zone is 180 ℃, the temperature in the third zone is 190 ℃, the temperature in the fourth zone is 195 ℃ and the temperature in the fifth zone is 200 ℃.
Comparative example 4
The preparation method of the starch-based degradable desorption tube material comprises the following steps:
(1) grinding 0.4 part of cyclodextrin for 15min to obtain uniformly dispersed nucleating agent powder A;
(2) blending 0.4 part of powder A, 28.3 parts of 100-mesh corn starch, 0.6 part of erucamide and 0.5 part of hyperbranched resin in a cold mixer at low speed for 5min to obtain uniformly blended powder B;
(3) adding 64 parts of PLA and 0.35 part of PBAT into high-speed mixing, carrying out high-speed blending for 20min, uniformly adding 4 parts of PBAT and 3 parts of glycerol triacetate while stirring in the process of blending the mixture, and carrying out high-speed blending for 10min to obtain a mixture C;
(4) adding the powder B and the mixture C into a high-speed mixer, and mixing at a high speed for 10min to obtain a blend D;
(5) melt-extruding and granulating the blend D to obtain the starch-based degradable granular material E; the melt extrusion conditions include: the temperature of the first zone is 170 ℃, the temperature of the second zone is 180 ℃, the temperature of the third zone is 190 ℃, the temperature of the fourth zone is 195 ℃ and the temperature of the fifth zone is 200 ℃; the rotating speed of the screw is 200-350 rpm/min;
(6) adding the degradable particles E into a single-screw straw extruder to extrude and draw a pipe to obtain a starch-based degradable straw, wherein the conditions of extruding and drawing the pipe comprise: the temperature in the first zone is 170 ℃, the temperature in the second zone is 180 ℃, the temperature in the third zone is 190 ℃, the temperature in the fourth zone is 195 ℃ and the temperature in the fifth zone is 200 ℃.
Comparative example 5
The preparation method of the starch-based degradable desorption tube material comprises the following steps:
(1) grinding 0.15 part of sebacic acid dibenzoylhydrazine and 0.25 part of cyclodextrin particles in a mortar for 15min to obtain uniformly dispersed nucleating agent powder A;
(2) blending 0.4 part of powder A, 28.7 parts of 100-mesh corn starch and 0.6 part of erucamide in a cold mixer at low speed for 5min to obtain uniformly blended powder B;
(3) adding 64 parts of PLA and 0.35 part of PBAT into high-speed mixing, carrying out high-speed blending for 20min, uniformly adding 4 parts of PBAT and 3 parts of glycerol triacetate while stirring in the process of blending the mixture, and carrying out high-speed blending for 10min to obtain a mixture C;
(4) adding the powder B and the mixture C into a high-speed mixer, and mixing at a high speed for 10min to obtain a blend D;
(5) melt-extruding and granulating the blend D to obtain the starch-based degradable granular material E; the melt extrusion conditions include: the temperature of the first zone is 170 ℃, the temperature of the second zone is 180 ℃, the temperature of the third zone is 190 ℃, the temperature of the fourth zone is 195 ℃ and the temperature of the fifth zone is 200 ℃; the rotating speed of the screw is 200-350 rpm/min;
(6) adding the degradable particles E into a single-screw straw extruder to extrude and draw a pipe to obtain a starch-based degradable straw, wherein the conditions of extruding and drawing the pipe comprise: the temperature in the first zone is 170 ℃, the temperature in the second zone is 180 ℃, the temperature in the third zone is 190 ℃, the temperature in the fourth zone is 195 ℃ and the temperature in the fifth zone is 200 ℃.
Performance detection
The starch-based degradable desorption tube materials prepared in examples 1-5 and comparative examples 1-5 are subjected to performance detection; tensile properties were measured in accordance with GB/T1040-1992 standards, flexural properties were measured in accordance with GB/T9341-2000 standards, impact properties were measured in accordance with GB/T1043-1992 standards, melt index was measured in accordance with GB/T3682-2000 standards, Vicat softening temperature was measured in accordance with GB/T19466.2-2004 standards, and relative biodegradability was measured in accordance with ASTM D6400/EN13432 standards, with the results shown in Table 1.
TABLE 1
| Item | Tensile strength | Modulus of elasticity | Elongation at break | Impact strength | Melt index | Vicat softening temperature | Relative rate of biological decomposition |
| Example 1 | 46.82MPa | 3039MPa | 2.28％ | 2.69KJ/m2 | 5.9g/10min | 88.3℃ | ＞90％ |
| Example 2 | 46.93MPa | 3346MPa | 3.27％ | 3.34KJ/m2 | 5.7g/10min | 90.1℃ | ＞90％ |
| Example 3 | 48.68MPa | 3363MPa | 2.81％ | 2.88KJ/m2 | 6.4g/10min | 89.9℃ | ＞90％ |
| Example 4 | 55MPa | 3200MPa | 5％ | 7.5KJ/m2 | 4.7g/10min | 92℃ | ＞90％ |
| Example 5 | 54.21MPa | 3269MPa | 4.92％ | 7.58KJ/m2 | 5.6g/10min | 90.6℃ | ＞90％ |
| Comparative example 1 | 60.13MPa | 2777MPa | 2.98％ | 3.35KJ/m2 | 4.2g/10min | 87.8℃ | ＞90％ |
| Comparative example 2 | 46.57MPa | 3378MPa | 2.14％ | 2.32KJ/m2 | 3.7g/10min | 88℃ | ＞90％ |
| Comparative example 3 | 54MPa | 3199MPa | 4.8％ | 6.7KJ/m2 | 4.6g/10min | 85℃ | ＞90％ |
| Comparative example 4 | 53.9MPa | 3200MPa | 4.6％ | 6.5KJ/m2 | 3.5g/10min | 86℃ | ＞90％ |
| Comparative example 5 | 55MPa | 3200MPa | 5％ | 7.5KJ/m2 | 3.8g/10min | 92℃ | ＞90％ |
In summary, the following steps: through compounding sebacic acid dibenzoyl hydrazine, cyclodextrin and PLA, the PLA composite material has good compatibility with PLA, and the crystallization rate of the PLA is accelerated in a range of lower addition amount, so that the heat resistance is improved; the glycerol triacetate, the tributyl citrate and the PBAT are blended and compounded with the polylactic acid, so that the brittleness of the PLA can be reduced, and the toughness of the PLA can be improved; starch is adopted as filling for compounding with PLA, so that the material cost is greatly reduced while the biodegradability is ensured; the method has simple process and mild operation condition, and is suitable for industrial large-scale production.
Claims (10)
1. The starch-based degradable desorption tube material is characterized by comprising the following components in parts by weight:
60-80 parts of PLA, 3-7 parts of PBAT, 5-30 parts of starch, 3-10 parts of plasticizer, 0.5-1 part of nucleating agent, 0.5-1 part of erucamide and 0.5-2 parts of hyperbranched assistant;
wherein the optical purity of the PLA is 95-100%, and the melt index (190 ℃, 2.16kg) of the PLA is 2-8g/10 min.
2. The starch-based degradable desorption tube material as claimed in claim 1, which comprises the following components in parts by weight:
65-70 parts of PLA, 3-7 parts of PBAT, 5-30 parts of starch, 3-10 parts of plasticizer, 0.5-1 part of nucleating agent, 0.5-1 part of erucamide and 0.5-2 parts of hyperbranched assistant;
wherein the optical purity of the PLA is more than or equal to 99.9 percent, and the melt index (190 ℃, 2.16kg) of the PLA is 3-7g/10 min.
3. The starch-based degradable straw material of claim 1, wherein the PBAT has a melt index of 3-6g/10min (190 ℃, 2.16 kg).
4. The starch-based degradable desorption tube material as claimed in claim 1, wherein the starch is one or a blend of corn starch and cassava starch, the starch mesh number is larger than or equal to 100 meshes, and the whiteness is larger than or equal to 90%.
5. The starch-based degradable release tube material of claim 1, wherein the plasticizer is one or a blend of glycerol triacetate and tributyl citrate.
6. The starch-based degradable desorption tube material of claim 1, wherein the nucleating agent is one or a mixture of potassium benzene sulfonate, zinc phenyl phosphate, dibenzoylhydrazide sebacate, organic phosphate and cyclodextrin.
7. The starch-based degradable desorption tube material as claimed in claim 1, wherein the nucleating agent is a blend of dibenzoylhydrazide sebacate and cyclodextrin, the erucamide is selected from one of PMC model of ArmoslipE, Poa prata (Croda), Korean Pathwel, and the hyperbranched assistant is solid powder with melting range of 145-155 ℃.
8. A method for preparing a starch-based degradable desorption tube material according to any one of claims 1-7, which comprises the following steps:
grinding the nucleating agent particles in a mortar to obtain uniformly dispersed nucleating agent powder A;
mixing the powder A, the starch, the erucamide and the hyperbranched auxiliary agent in a cold mixer to obtain uniformly mixed powder B;
adding PLA and PBAT into a high-speed mixer, blending for 20min, uniformly adding a plasticizer while stirring in the process of blending the mixture, and blending for 10min to obtain a mixture C;
adding the powder B and the powder C into a high-speed mixer, and mixing for 10min to obtain a blend D;
adding the blend D into a double-screw extruder for melt extrusion granulation to obtain starch-based degradable straw material particles E;
and adding the degradable particles E into a single-screw straw, extruding and pulling the straw to obtain the starch-based degradable straw.
9. The method as claimed in claim 8, wherein the temperature of the granulating and tube-drawing is 160-205 ℃.
10. The method for preparing a starch-based degradable straw material according to claim 9, wherein the conditions for granulating and extruding the straw comprise: the temperature of the first zone is 170 +/-5 ℃, the temperature of the second zone is 180 +/-5 ℃, the temperature of the third zone is 190 +/-5 ℃, the temperature of the fourth zone is 195 +/-5 ℃ and the temperature of the fifth zone is 200 +/-5 ℃.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114561092A (en) * | 2022-03-24 | 2022-05-31 | 南京柯支机电设备有限公司 | Crystallization method for producing degradable material beverage straw |
| CN115746523A (en) * | 2022-11-16 | 2023-03-07 | 深圳市鼎力盛科技有限公司 | Novel material air column bag with strong degradation capability and preparation method thereof |
| TWI804197B (en) * | 2022-02-17 | 2023-06-01 | 紀騰縈 | Manufacturing method of bogot eco-friendly material |
| CN118667312A (en) * | 2024-06-14 | 2024-09-20 | 东莞市康源新材料有限公司 | Degradable environment-friendly straw and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103450648A (en) * | 2012-06-05 | 2013-12-18 | 上海杰事杰新材料(集团)股份有限公司 | Biodegradable polylactic acid/starch compound material and preparation method thereof |
| CN103627153A (en) * | 2012-08-20 | 2014-03-12 | 上海杰事杰新材料(集团)股份有限公司 | Entire biodegradation PLA/PBAT composite material and preparing method therefor |
| CN110128806A (en) * | 2019-06-10 | 2019-08-16 | 中山市正合色彩资源有限公司 | A kind of heat-resistance polylactic acid composite material and preparation method thereof of short degradation cycle |
| CN110845830A (en) * | 2019-11-13 | 2020-02-28 | 青岛润兴塑料新材料有限公司 | Starch filled PLA/PBAT full-biodegradable composite material and preparation method thereof |
-
2021
- 2021-11-04 CN CN202111298092.2A patent/CN114031909A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103450648A (en) * | 2012-06-05 | 2013-12-18 | 上海杰事杰新材料(集团)股份有限公司 | Biodegradable polylactic acid/starch compound material and preparation method thereof |
| CN103627153A (en) * | 2012-08-20 | 2014-03-12 | 上海杰事杰新材料(集团)股份有限公司 | Entire biodegradation PLA/PBAT composite material and preparing method therefor |
| CN110128806A (en) * | 2019-06-10 | 2019-08-16 | 中山市正合色彩资源有限公司 | A kind of heat-resistance polylactic acid composite material and preparation method thereof of short degradation cycle |
| CN110845830A (en) * | 2019-11-13 | 2020-02-28 | 青岛润兴塑料新材料有限公司 | Starch filled PLA/PBAT full-biodegradable composite material and preparation method thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI804197B (en) * | 2022-02-17 | 2023-06-01 | 紀騰縈 | Manufacturing method of bogot eco-friendly material |
| CN114561092A (en) * | 2022-03-24 | 2022-05-31 | 南京柯支机电设备有限公司 | Crystallization method for producing degradable material beverage straw |
| CN115746523A (en) * | 2022-11-16 | 2023-03-07 | 深圳市鼎力盛科技有限公司 | Novel material air column bag with strong degradation capability and preparation method thereof |
| CN115746523B (en) * | 2022-11-16 | 2024-12-10 | 深圳市鼎力盛科技有限公司 | A kind of air column bag with strong degradation ability and preparation method thereof |
| CN118667312A (en) * | 2024-06-14 | 2024-09-20 | 东莞市康源新材料有限公司 | Degradable environment-friendly straw and preparation method thereof |
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