CN112457639A - Polylactic resin prepared from corn and preparation method thereof - Google Patents
Polylactic resin prepared from corn and preparation method thereof Download PDFInfo
- Publication number
- CN112457639A CN112457639A CN202011283435.3A CN202011283435A CN112457639A CN 112457639 A CN112457639 A CN 112457639A CN 202011283435 A CN202011283435 A CN 202011283435A CN 112457639 A CN112457639 A CN 112457639A
- Authority
- CN
- China
- Prior art keywords
- corn
- polylactic acid
- solution
- polylactic
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/24—Crystallisation aids
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the technical field of polylactic acid resin, in particular to polylactic acid resin prepared from corn and a preparation method thereof. The feed comprises the following raw materials: the polylactic acid resin prepared from corn prepared by the invention can greatly improve the crystallization nucleation density, accelerate the crystallization speed, improve the crystallinity, and improve the heat resistance, the formability and other properties of the product by adding the nucleating agent into the polylactic acid.
Description
Technical Field
The invention relates to the technical field of polylactic acid resin, in particular to polylactic acid resin prepared from corn and a preparation method thereof.
Background
Polylactic acid (PLA) is a novel biodegradable material, is prepared from starch raw materials provided by renewable plant resources, is saccharified to obtain glucose, is fermented by the glucose and certain strains to prepare high-purity lactic acid, and is synthesized into polylactic acid with a certain molecular weight by a chemical synthesis method. The common plastic treatment method still comprises the steps of burning and cremating to cause a large amount of greenhouse gases to be discharged into the air, the polylactic acid plastic is buried in soil to be degraded, the generated carbon dioxide directly enters soil organic matters or is absorbed by plants, the carbon dioxide is not discharged into the air and does not cause greenhouse effect, and the preservative film prepared from the polylactic acid resin has good air permeability, oxygen permeability and carbon dioxide permeability and also has the characteristic of odor isolation;
however, the molecular weight of the existing polylactic acid resin is low, so that the application range of the resin is reduced, the polylactic acid resin has limitations and poor mechanical properties, the processing performance and the application of the polylactic acid resin are influenced, the ageing resistance of the polylactic acid resin is poor due to the degradability of the polylactic acid resin, the ageing speed of the product is accelerated, and the mechanical properties of the aged polylactic acid product are gradually reduced.
Disclosure of Invention
The invention aims to provide polylactic resin prepared from corn and a preparation method thereof, so as to solve the problems in the background technology.
In order to achieve the above objects, in one aspect, the present invention provides a polylactic acid resin prepared from corn, comprising the following raw materials: 90-110 parts of polylactic acid, 1-20 parts of nucleating agent, 15-30 parts of plasticizer, 30-50 parts of filler and 1-5 parts of antioxidant.
As a further improvement of the technical scheme, the polylactic acid is produced by a solution polymerization method through D, L-lactic acid, a solution and a catalyst, the solution is diphenyl ether, the catalyst is tin powder, and the generation method comprises the following steps:
s1.1, adding D, L lactic acid, a solution and a catalyst into a reactor, heating to 110 ℃ at 100-;
s1.2, raising the temperature to 120-130 ℃, reducing the pressure to 3800-4200Pa, and performing dehydration to prepare the high molecular weight polylactic acid with the molecular weight of 18-22 ten thousand.
As a further improvement of the technical scheme, the extraction method of the D, L lactic acid comprises the following steps:
s2.1, cleaning corn, soaking, coarsely crushing and grinding to obtain corn paste;
s2.2, adding the corn paste into screening equipment, and screening corn fibers;
s2.3, adding the screened corn paste into a launder, and separating protein to obtain corn starch;
s2.4, repeatedly cleaning the corn starch for 2-3 times, and dehydrating and drying to obtain a finished product of corn starch;
and S2.5, fermenting the finished product corn starch to obtain the D, L lactic acid.
As a further improvement of the technical scheme, the nucleating agent is selected from at least one of 4, 6-di-tert-butylphenyl sodium phosphate, sodium 2, 2-methylenebis (4, 6-di-tert-butylphenyl) phosphate and aluminum salt, and the nucleating agent is added in the industrial application of polylactic acid, so that the crystallization nucleating density can be greatly improved, the crystallization speed can be increased, the crystallinity can be improved, the heat resistance, the formability and other properties of a product can be improved, and the melting point of the nucleating agent is higher than that of the polylactic acid and has certain compatibility with the polylactic acid.
As a further improvement of the technical scheme, the plasticizer is selected from at least one of glyceryl triacetate, tributyl citrate, acetyl tributyl citrate, dioctyl phthalate, polyethylene glycol, gluconate and glycerol, and the plasticizer is added to reduce the glass transition temperature of the polylactic acid composite material and increase the flexibility and the elongation of the material.
As a further improvement of the technical scheme, the filler is starch, preferably, the third component, namely diphenylmethane diisocyanate, is used as an auxiliary agent, the starch is a naturally degradable hydrophilic material, the blend of the starch and polylactic acid can be completely biodegraded, the polylactic acid in the blend of the starch and the polylactic acid exists as a continuous parent phase, the starch is used as the filler, the water resistance and the mechanical property of the blending system can be improved, the interfacial adhesion between the polylactic acid and the starch is reduced along with the aging of the blend, and the diphenylmethane diisocyanate can improve the interfacial adhesion, so that the aging of the polylactic acid/starch blend is delayed, and the reduction of the mechanical property is delayed.
As a further improvement of the technical scheme, the antioxidant is at least one of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate and tris (2, 4-di-tert-butylphenyl) phosphite, and the antioxidant can effectively prevent the thermal oxidative degradation of the polymer material in the long-term aging process, is also an efficient processing stabilizer and can improve the discoloration resistance of the polymer material under the high-temperature processing condition.
In another aspect, the present invention provides a method for preparing polylactic acid resin from corn, comprising any one of the above steps of:
s3.1, adding polylactic acid into a reaction kettle, and heating and melting;
s3.2, heating, adding a filling agent and an auxiliary agent, and uniformly stirring to obtain a solution a;
s3.3, adding a nucleating agent and a plasticizer into the solution a, and uniformly stirring;
s3.4, adding an antioxidant into the solution a, and uniformly stirring to obtain a solution b
And S3.5, adding the solution b into a double-screw extruder for extrusion to obtain the polylactic resin.
Preferably, in S3.1, the temperature of the reaction kettle is 70-90 ℃, in S3.2-S3.4, the temperature of the reaction kettle is 110-.
Preferably, in S3.5, the extrusion temperature of the twin-screw extruder is 180-230 ℃.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the polylactic resin prepared from the corn and the preparation method thereof, the nucleating agent is added into the polylactic acid, so that the crystallization nucleation density can be greatly improved, the crystallization speed is accelerated, the crystallinity is improved, and the performances of the product, such as heat resistance, moldability and the like, can be improved.
2. In the polylactic resin prepared from the corn and the preparation method thereof, the starch is used as a filler to be blended with the polylactic acid, so that the water resistance and the mechanical property of a blending system can be improved.
3. In the polylactic resin prepared from the corn and the preparation method thereof, the interfacial adhesion between polylactic acid and starch is reduced along with the aging of the blend, and the diphenylmethane diisocyanate can improve the interfacial adhesion, so that the aging of the polylactic acid/starch blend is delayed, and the reduction of the mechanical property is delayed.
4. In the polylactic resin prepared from the corn and the preparation method thereof, the antioxidant is added, so that the thermal oxidation degradation of the polymer material in a long-term aging process can be effectively prevented, and the polylactic resin is an efficient processing stabilizer and can improve the color change resistance of the polymer material under a high-temperature processing condition.
Drawings
Fig. 1 is an overall flow chart of embodiment 1.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious 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.
Example 1A polylactic acid resin prepared from corn and a method for preparing the same, comprising
Firstly, preparation of raw materials
(1) And (3) generation of lactic acid: cleaning semen Maydis, soaking, coarse pulverizing, and grinding to obtain semen Maydis paste; adding the corn paste into a screening device, and screening corn fibers; adding the screened corn paste into a launder, and separating protein to prepare corn starch; repeatedly cleaning the corn starch for 2-3 times, and dehydrating and drying to obtain the finished product corn starch; fermenting the finished product corn starch to obtain D, L lactic acid;
(2) preparing raw materials: adding D, L lactic acid, the solution and a catalyst into a reactor, heating to 110 ℃ under the pressure of 4500-.
Secondly, preparation of corn polylactic resin
(1) Blending raw materials: adding 90 parts of polylactic acid into a reaction kettle, heating to 70-90 ℃ for melting, heating to 110-130 ℃, stirring at a speed of 80-100r/min, adding 30 parts of filler and auxiliary agent, stirring uniformly to obtain a solution a, adding 1 part of nucleating agent and 15 parts of plasticizer into the solution a, stirring uniformly, adding 1 part of antioxidant into the solution a, and stirring uniformly to obtain a solution b;
(2) extruding resin: and adding the solution b into a double-screw extruder for extrusion, wherein the extrusion temperature of the double-screw extruder is 180-230 ℃, and preparing the polylactic resin.
Example 2A polylactic acid resin prepared from corn and a method for preparing the same, comprising
Firstly, preparation of raw materials
(1) And (3) generation of lactic acid: cleaning semen Maydis, soaking, coarse pulverizing, and grinding to obtain semen Maydis paste; adding the corn paste into a screening device, and screening corn fibers; adding the screened corn paste into a launder, and separating protein to prepare corn starch; repeatedly cleaning the corn starch for 2-3 times, and dehydrating and drying to obtain the finished product corn starch; fermenting the finished product corn starch to obtain D, L lactic acid;
(2) preparing raw materials: adding D, L lactic acid, the solution and a catalyst into a reactor, heating to 110 ℃ under the pressure of 4500-.
Secondly, preparation of corn polylactic resin
(1) Blending raw materials: adding 95 parts of polylactic acid into a reaction kettle, heating to 70-90 ℃ for melting, heating to 110-130 ℃, stirring at 80-100r/min, adding 35 parts of filler and auxiliary agent, uniformly stirring to obtain a solution a, adding 5 parts of nucleating agent and 18.8 parts of plasticizer into the solution a, uniformly stirring, adding 2 parts of antioxidant into the solution a, and uniformly stirring to obtain a solution b;
(2) extruding resin: and adding the solution b into a double-screw extruder for extrusion, wherein the extrusion temperature of the double-screw extruder is 180-230 ℃, and preparing the polylactic resin.
Example 3A polylactic acid resin prepared from corn and a method for preparing the same, comprising
Firstly, preparation of raw materials
(1) And (3) generation of lactic acid: cleaning semen Maydis, soaking, coarse pulverizing, and grinding to obtain semen Maydis paste; adding the corn paste into a screening device, and screening corn fibers; adding the screened corn paste into a launder, and separating protein to prepare corn starch; repeatedly cleaning the corn starch for 2-3 times, and dehydrating and drying to obtain the finished product corn starch; fermenting the finished product corn starch to obtain D, L lactic acid;
(2) preparing raw materials: adding D, L lactic acid, the solution and a catalyst into a reactor, heating to 110 ℃ under the pressure of 4500-.
Secondly, preparation of corn polylactic resin
(1) Blending raw materials: adding 100 parts of polylactic acid into a reaction kettle, heating to 70-90 ℃ for melting, heating to 110-130 ℃, stirring at a speed of 80-100r/min, adding 40 parts of filler and auxiliary agent, uniformly stirring to obtain a solution a, adding 10 parts of nucleating agent and 22.5 parts of plasticizer into the solution a, uniformly stirring, adding 3 parts of antioxidant into the solution a, and uniformly stirring to obtain a solution b;
(2) extruding resin: and adding the solution b into a double-screw extruder for extrusion, wherein the extrusion temperature of the double-screw extruder is 180-230 ℃, and preparing the polylactic resin.
Example 4A polylactic acid resin prepared from corn and a method for preparing the same, comprising
Firstly, preparation of raw materials
(1) And (3) generation of lactic acid: cleaning semen Maydis, soaking, coarse pulverizing, and grinding to obtain semen Maydis paste; adding the corn paste into a screening device, and screening corn fibers; adding the screened corn paste into a launder, and separating protein to prepare corn starch; repeatedly cleaning the corn starch for 2-3 times, and dehydrating and drying to obtain the finished product corn starch; fermenting the finished product corn starch to obtain D, L lactic acid;
(2) preparing raw materials: adding D, L lactic acid, the solution and a catalyst into a reactor, heating to 110 ℃ under the pressure of 4500-.
Secondly, preparation of corn polylactic resin
(1) Blending raw materials: adding 105 parts of polylactic acid into a reaction kettle, heating to 70-90 ℃ for melting, heating to 110-130 ℃, stirring at a speed of 80-100r/min, adding 45 parts of filler and auxiliary agent, uniformly stirring to obtain a solution a, adding 15 parts of nucleating agent and 26.5 parts of plasticizer into the solution a, uniformly stirring, adding 4 parts of antioxidant into the solution a, and uniformly stirring to obtain a solution b;
(2) extruding resin: and adding the solution b into a double-screw extruder for extrusion, wherein the extrusion temperature of the double-screw extruder is 180-230 ℃, and preparing the polylactic resin.
Example 5A polylactic acid resin prepared from corn and a method for preparing the same, comprising
Firstly, preparation of raw materials
(1) And (3) generation of lactic acid: cleaning semen Maydis, soaking, coarse pulverizing, and grinding to obtain semen Maydis paste; adding the corn paste into a screening device, and screening corn fibers; adding the screened corn paste into a launder, and separating protein to prepare corn starch; repeatedly cleaning the corn starch for 2-3 times, and dehydrating and drying to obtain the finished product corn starch; fermenting the finished product corn starch to obtain D, L lactic acid;
(2) preparing raw materials: adding D, L lactic acid, the solution and a catalyst into a reactor, heating to 110 ℃ under the pressure of 4500-.
Secondly, preparation of corn polylactic resin
(1) Blending raw materials: adding 110 parts of polylactic acid into a reaction kettle, heating to 70-90 ℃ for melting, heating to 110-130 ℃, stirring at a speed of 80-100r/min, adding 50 parts of filler and auxiliary agent, stirring uniformly to obtain a solution a, adding 20 parts of nucleating agent and 30 parts of plasticizer into the solution a, stirring uniformly, adding 5 parts of antioxidant into the solution a, and stirring uniformly to obtain a solution b;
(2) extruding resin: and adding the solution b into a double-screw extruder for extrusion, wherein the extrusion temperature of the double-screw extruder is 180-230 ℃, and preparing the polylactic resin.
The nucleating agent is selected from at least one of 4, 6-di-tert-butylphenyl sodium phosphate, 2-methylenebis (4, 6-di-tert-butylphenyl) phosphate sodium salt and aluminum salt, and is added in the industrial application of polylactic acid, so that the nucleating agent can greatly improve the crystallization nucleation density, accelerate the crystallization speed, improve the crystallinity, improve the heat resistance, the moldability and other properties of the product, has a higher melting point than that of the polylactic acid, and has certain compatibility with the polylactic acid;
the plasticizer is selected from at least one of glyceryl triacetate, tributyl citrate, acetyl tributyl citrate, dioctyl phthalate, polyethylene glycol, gluconate and glycerol, and the plasticizer is added to reduce the glass transition temperature of the polylactic acid composite material and increase the flexibility and the elongation of the material;
the filler is starch, preferably the third component, namely diphenylmethane diisocyanate, is used as an auxiliary agent, the starch is a naturally degradable hydrophilic material, the blend of the starch and polylactic acid can be completely biodegraded, the polylactic acid exists as a continuous parent phase in the blend of the starch and the polylactic acid, the starch is used as the filler, the water resistance and the mechanical property of a blending system can be improved, the interfacial adhesion between the polylactic acid and the starch is reduced along with the aging of the blend, and the diphenylmethane diisocyanate can improve the interfacial adhesion, so that the aging of the polylactic acid/starch blend is delayed, and the reduction of the mechanical property is delayed;
the antioxidant is at least one of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate and tris (2, 4-di-tert-butylphenyl) phosphite, can effectively prevent thermal oxidative degradation of the polymer material in a long-term aging process, is also an efficient processing stabilizer, and can improve the discoloration resistance of the polymer material under high-temperature processing conditions.
In the polylactic resin prepared from the corn, the polylactic resin has good mechanical property and strong ageing resistance, and the detection indexes of the polylactic resin prepared from the corn are shown in table 1:
TABLE 1
Tensile Strength (MPa) | Elongation at Break (%) | Heat resistance (. degree.C.) | Degree of aging after 90 days | |
Example 1 | 17 | 142 | 160 | No phenomenon |
Example 2 | 19 | 165 | 170 | No phenomenon |
Example 3 | 22 | 201 | 180 | No phenomenon |
Example 4 | 20 | 189 | 178 | No phenomenon |
Example 5 | 18 | 178 | 178 | No phenomenon |
As shown in table 1, in the polylactic acid resin prepared from corn prepared by the present invention, in examples 1 to 5, when 100 parts of polylactic acid, 40 parts of filler, 10 parts of nucleating agent and 22.5 parts of plasticizer are used, the tensile strength and elongation at break of the polylactic acid resin are the best, and thus it can be seen that the polylactic acid blended by the filler, the nucleating agent and the plasticizer has better mechanical properties;
in examples 1 to 5, the polylactic acid resin did not age after 90 days, and when 10 parts of the nucleating agent and 3 parts of the antioxidant were used, the heat-resistant temperature of the polylactic acid resin was the highest, so it can be seen that the amount of the nucleating agent and the antioxidant added in example 3 has a great influence on the aging resistance of the polylactic acid resin.
Comparative example 1 a polylactic acid resin prepared from corn and a method for preparing the same, comprising
Firstly, preparation of raw materials
(1) And (3) generation of lactic acid: cleaning semen Maydis, soaking, coarse pulverizing, and grinding to obtain semen Maydis paste; adding the corn paste into a screening device, and screening corn fibers; adding the screened corn paste into a launder, and separating protein to prepare corn starch; repeatedly cleaning the corn starch for 2-3 times, and dehydrating and drying to obtain the finished product corn starch; fermenting the finished product corn starch to obtain D, L lactic acid;
(2) preparing raw materials: adding D, L lactic acid, the solution and a catalyst into a reactor, heating to 110 ℃ under the pressure of 4500-.
Secondly, preparation of corn polylactic resin
(1) Blending raw materials: adding 100 parts of polylactic acid into a reaction kettle, heating to 70-90 ℃ for melting, heating to 110-130 ℃, stirring at the speed of 80-100r/min, adding 40 parts of filler and an auxiliary agent, uniformly stirring to obtain a solution a, adding 22.5 parts of plasticizer into the solution a, uniformly stirring, adding 3 parts of antioxidant into the solution a, and uniformly stirring to obtain a solution b;
(2) extruding resin: and adding the solution b into a double-screw extruder for extrusion, wherein the extrusion temperature of the double-screw extruder is 180-230 ℃, and preparing the polylactic resin.
Comparative example 2 polylactic acid resin prepared from corn and a method for preparing the same comprising
Firstly, preparation of raw materials
(1) And (3) generation of lactic acid: cleaning semen Maydis, soaking, coarse pulverizing, and grinding to obtain semen Maydis paste; adding the corn paste into a screening device, and screening corn fibers; adding the screened corn paste into a launder, and separating protein to prepare corn starch; repeatedly cleaning the corn starch for 2-3 times, and dehydrating and drying to obtain the finished product corn starch; fermenting the finished product corn starch to obtain D, L lactic acid;
(2) preparing raw materials: adding D, L lactic acid, the solution and a catalyst into a reactor, heating to 110 ℃ under the pressure of 4500-.
Secondly, preparation of corn polylactic resin
(1) Blending raw materials: adding 100 parts of polylactic acid into a reaction kettle, heating to 70-90 ℃ for melting, heating to 110-130 ℃, stirring at 80-100r/min, adding 40 parts of filler and auxiliary agent, uniformly stirring to obtain a solution a, adding 22.5 parts of plasticizer into the solution a, and uniformly stirring to obtain a solution b;
(2) extruding resin: and adding the solution b into a double-screw extruder for extrusion, wherein the extrusion temperature of the double-screw extruder is 180-230 ℃, and preparing the polylactic resin.
Comparative example 3 polylactic acid resin prepared from corn and preparation method thereof, comprising
Firstly, preparation of raw materials
(1) And (3) generation of lactic acid: cleaning semen Maydis, soaking, coarse pulverizing, and grinding to obtain semen Maydis paste; adding the corn paste into a screening device, and screening corn fibers; adding the screened corn paste into a launder, and separating protein to prepare corn starch; repeatedly cleaning the corn starch for 2-3 times, and dehydrating and drying to obtain the finished product corn starch; fermenting the finished product corn starch to obtain D, L lactic acid;
(2) preparing raw materials: adding D, L lactic acid, the solution and a catalyst into a reactor, heating to 110 ℃ under the pressure of 4500-.
Secondly, preparation of corn polylactic resin
(1) Blending raw materials: adding 100 parts of polylactic acid into a reaction kettle, heating to 70-90 ℃ for melting, heating to 110-130 ℃, stirring at a speed of 80-100r/min, adding 40 parts of filler, uniformly stirring to obtain a solution a, adding 10 parts of nucleating agent and 22.5 parts of plasticizer into the solution a, uniformly stirring, adding 3 parts of antioxidant into the solution a, and uniformly stirring to obtain a solution b;
(2) extruding resin: and adding the solution b into a double-screw extruder for extrusion, wherein the extrusion temperature of the double-screw extruder is 180-230 ℃, and preparing the polylactic resin.
Comparative example 4 polylactic acid resin prepared from corn and method for preparing the same comprising
Firstly, preparation of raw materials
(1) And (3) generation of lactic acid: cleaning semen Maydis, soaking, coarse pulverizing, and grinding to obtain semen Maydis paste; adding the corn paste into a screening device, and screening corn fibers; adding the screened corn paste into a launder, and separating protein to prepare corn starch; repeatedly cleaning the corn starch for 2-3 times, and dehydrating and drying to obtain the finished product corn starch; fermenting the finished product corn starch to obtain D, L lactic acid;
(2) preparing raw materials: adding D, L lactic acid, the solution and a catalyst into a reactor, heating to 110 ℃ under the pressure of 4500-.
Secondly, preparation of corn polylactic resin
(1) Blending raw materials: adding 100 parts of polylactic acid into a reaction kettle, heating to 70-90 ℃ for melting, heating to 110-130 ℃, stirring at 80-100r/min, adding 10 parts of nucleating agent and 22.5 parts of plasticizer, uniformly stirring to obtain a solution a, adding 3 parts of antioxidant into the solution a, and uniformly stirring to obtain a solution b;
(2) extruding resin: and adding the solution b into a double-screw extruder for extrusion, wherein the extrusion temperature of the double-screw extruder is 180-230 ℃, and preparing the polylactic resin.
The polylactic resin prepared from the corn has good heat resistance, ageing resistance and mechanical property, has a great relationship with a nucleating agent, a filling agent, an auxiliary agent and an antioxidant which are added into the polylactic resin, and in order to verify the related technical scheme, the applicant performs the following tests:
comparative examples 1 to 4: by adopting the method of example 3, the related indexes of the polylactic acid resin prepared from the prepared corn are detected under the condition of removing the nucleating agent, the filling agent, the auxiliary agent and the antioxidant, and the specific indexes are shown in table 2:
TABLE 2
According to table 2, in comparative examples 1 to 4, the tensile strength and elongation at break of the polylactic acid resin are decreased when the nucleating agent and the filler are removed, and it can be seen that the nucleating agent and the filler affect the mechanical properties of the polylactic acid resin, and the tensile strength and elongation at break of the polylactic acid resin are greatly decreased after 90 days when the nucleating agent and the antioxidant are removed simultaneously, and the heat resistance temperature is decreased, so it can be seen that the nucleating agent and the antioxidant are important factors affecting the heat resistance and the aging resistance of the polylactic acid resin;
in comparative example 3, the aging phenomenon of the polylactic acid resin was more remarkable with the removal of the adjuvant, and thus it can be seen that the addition of the adjuvant when the filler is blended with the polylactic acid is also a large factor affecting the aging resistance of the polylactic acid resin.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and the preferred embodiments of the present invention are described in the above embodiments and the description, and are not intended to limit the present invention. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. Polylactic resin prepared from corn comprises the following raw materials: 90-110 parts of polylactic acid, 1-20 parts of nucleating agent, 15-30 parts of plasticizer, 30-50 parts of filler and 1-5 parts of antioxidant.
2. Polylactic acid resin made from corn according to claim 1, characterized in that: the polylactic acid is produced by a solution polymerization method through D, L-lactic acid, a solution and a catalyst, wherein the solution is diphenyl ether, the catalyst is tin powder, and the generation method comprises the following steps:
s1.1, adding D, L lactic acid, a solution and a catalyst into a reactor, heating to 110 ℃ at 100-;
s1.2, raising the temperature to 120-130 ℃, reducing the pressure to 3800-4200Pa, and performing dehydration to prepare the high molecular weight polylactic acid with the molecular weight of 18-22 ten thousand.
3. Polylactic acid resin made from corn according to claim 1, characterized in that: the extraction method of the D, L lactic acid comprises the following steps:
s2.1, cleaning corn, soaking, coarsely crushing and grinding to obtain corn paste;
s2.2, adding the corn paste into screening equipment, and screening corn fibers;
s2.3, adding the screened corn paste into a launder, and separating protein to obtain corn starch;
s2.4, repeatedly cleaning the corn starch for 2-3 times, and dehydrating and drying to obtain a finished product of corn starch;
and S2.5, fermenting the finished product corn starch to obtain the D, L lactic acid.
4. Polylactic acid resin made from corn according to claim 1, characterized in that: the nucleating agent is selected from at least one of 4, 6-di-tert-butylphenyl sodium phosphate, 2-methylenebis (4, 6-di-tert-butylphenyl) phosphate sodium salt and aluminum salt.
5. Polylactic acid resin made from corn according to claim 1, characterized in that: the plasticizer is at least one selected from glyceryl triacetate, tributyl citrate, acetyl tributyl citrate, dioctyl phthalate, polyethylene glycol, gluconate and glycerol.
6. Polylactic acid resin made from corn according to claim 1, characterized in that: the filler is starch, and preferably, a third component of diphenylmethane diisocyanate is used as an auxiliary agent.
7. Polylactic acid resin made from corn according to claim 1, characterized in that: the antioxidant is at least one of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate and tris (2, 4-di-tert-butylphenyl) phosphite.
8. A method for preparing polylactic resin prepared from corn, which comprises the polylactic resin prepared from corn according to any one of claims 1 to 7, and comprises the following operation steps:
s3.1, adding polylactic acid into a reaction kettle, and heating and melting;
s3.2, heating, adding a filling agent and an auxiliary agent, and uniformly stirring to obtain a solution a;
s3.3, adding a nucleating agent and a plasticizer into the solution a, and uniformly stirring;
s3.4, adding an antioxidant into the solution a, and uniformly stirring to obtain a solution b;
and S3.5, adding the solution b into a double-screw extruder for extrusion to obtain the polylactic resin.
9. The polylactic acid resin prepared from corn according to claim 8 and the preparation method thereof, wherein: in the S3.1, the temperature of the reaction kettle is 70-90 ℃, in the S3.2-S3.4, the temperature of the reaction kettle is 110-130 ℃, and the stirring speed is 80-100 r/min.
10. The polylactic acid resin prepared from corn according to claim 8 and the preparation method thereof, wherein: in the S3.5, the extrusion temperature of the double-screw extruder is 180-230 ℃.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202011283435.3A CN112457639A (en) | 2020-11-17 | 2020-11-17 | Polylactic resin prepared from corn and preparation method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202011283435.3A CN112457639A (en) | 2020-11-17 | 2020-11-17 | Polylactic resin prepared from corn and preparation method thereof |
Publications (1)
Publication Number | Publication Date |
---|---|
CN112457639A true CN112457639A (en) | 2021-03-09 |
Family
ID=74836132
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202011283435.3A Pending CN112457639A (en) | 2020-11-17 | 2020-11-17 | Polylactic resin prepared from corn and preparation method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN112457639A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113713185A (en) * | 2021-09-02 | 2021-11-30 | 浙江晟祺实业有限公司 | Biomedical degradable material and preparation method thereof |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008201863A (en) * | 2007-02-19 | 2008-09-04 | Hiroshima Pref Gov | Method for producing molded article of polylactic acid resin |
WO2010082639A1 (en) * | 2009-01-16 | 2010-07-22 | バイオベース株式会社 | Polylactic acid resin composition and additive for polylactic acid resin |
CN101983986A (en) * | 2010-10-26 | 2011-03-09 | 中国科学院长春应用化学研究所 | Transparent and toughening polylactic acid resin and method for preparing the same |
CN102134381A (en) * | 2011-04-29 | 2011-07-27 | 永康市南益生物科技有限公司 | Polylactic acid modified material and preparation method thereof |
CN102464873A (en) * | 2010-11-05 | 2012-05-23 | 中国石油化工股份有限公司 | Bidirectional stretching polylactic acid / montmorillonoid, and preparation method and application thereof |
CN103102661A (en) * | 2012-05-18 | 2013-05-15 | 杭州曦茂新材料科技有限公司 | Rapid nucleating agent for polylactic resin |
CN109134293A (en) * | 2018-08-14 | 2019-01-04 | 深圳前海蜗牛妈妈科技有限公司 | A kind of polylactic acid efficient nucleation agent and the preparation method and application thereof |
-
2020
- 2020-11-17 CN CN202011283435.3A patent/CN112457639A/en active Pending
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008201863A (en) * | 2007-02-19 | 2008-09-04 | Hiroshima Pref Gov | Method for producing molded article of polylactic acid resin |
WO2010082639A1 (en) * | 2009-01-16 | 2010-07-22 | バイオベース株式会社 | Polylactic acid resin composition and additive for polylactic acid resin |
CN101983986A (en) * | 2010-10-26 | 2011-03-09 | 中国科学院长春应用化学研究所 | Transparent and toughening polylactic acid resin and method for preparing the same |
CN102464873A (en) * | 2010-11-05 | 2012-05-23 | 中国石油化工股份有限公司 | Bidirectional stretching polylactic acid / montmorillonoid, and preparation method and application thereof |
CN102134381A (en) * | 2011-04-29 | 2011-07-27 | 永康市南益生物科技有限公司 | Polylactic acid modified material and preparation method thereof |
CN103102661A (en) * | 2012-05-18 | 2013-05-15 | 杭州曦茂新材料科技有限公司 | Rapid nucleating agent for polylactic resin |
CN109134293A (en) * | 2018-08-14 | 2019-01-04 | 深圳前海蜗牛妈妈科技有限公司 | A kind of polylactic acid efficient nucleation agent and the preparation method and application thereof |
Non-Patent Citations (4)
Title |
---|
李建军: "《塑料配方设计》", 31 May 2019, 中国轻工业出版社 * |
杨继全等: "《异质材料3D打印技术》", 30 March 2019, 华中科技大学出版社 * |
柴春鹏等: "《高分子合成材料学》", 31 January 2019, 北京理工大学出版社 * |
益小苏等: "《生物质树脂、纤维及生物复合材料》", 31 August 2017, 中国建材工业出版社 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113713185A (en) * | 2021-09-02 | 2021-11-30 | 浙江晟祺实业有限公司 | Biomedical degradable material and preparation method thereof |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN106832801B (en) | A kind of lignin modification PBAT biodegradable plastic and preparation method thereof | |
CN100497457C (en) | Degradable high polymer material of poplar wood pulp cellulose and its preparation method | |
CN109233162B (en) | Environment-friendly degradable composite film for packaging and preparation method thereof | |
CN110437590A (en) | A kind of starch-base biodegradation food package film and preparation method thereof that composite nano materials are modified | |
CN115584109B (en) | Composite material, preparation method and application thereof, and degradable mulching film | |
WO2020088214A1 (en) | Pha-modified tps/pbat biodegradable resin and preparation method therefor | |
CN112920571A (en) | Modified PLA (polylactic acid) and PHA (polyhydroxyalkanoate) blending material and preparation method thereof | |
CN112457639A (en) | Polylactic resin prepared from corn and preparation method thereof | |
CN110358273B (en) | Biomass antibacterial film with high puncture resistance | |
CN115433441A (en) | Full-biodegradable material and preparation method thereof | |
CN112063126B (en) | Completely biodegradable starch composite mulching film and preparation method thereof | |
CN112812518A (en) | Thermoplastic biodegradable plastic and preparation method thereof | |
CN106751628A (en) | A kind of polylactic acid membrane and preparation method thereof | |
CN112210198A (en) | Biodegradable composite material, preparation method thereof and application thereof in production of mulching film | |
CN112322001A (en) | Impact-resistant modified PET plastic and preparation method thereof | |
CN108948680A (en) | A kind of full biology base PBSA biodegradable plastic of starch conversion and preparation method thereof | |
CN112175361A (en) | High-barrier stretch-resistant antibacterial film type degradable material and preparation method thereof | |
CN116731489A (en) | Degradable antibacterial composite preservative film and preparation method thereof | |
CN111621127A (en) | Polyethylene glycol modified PHA composite material and preparation method thereof | |
CN115197557B (en) | Low-carbon bio-based full-degradable film material and preparation method thereof | |
CN109735067A (en) | A kind of lignin-base biodegradable plastics and preparation method thereof | |
CN115028899A (en) | Degradable environment-friendly antibacterial tableware and preparation process thereof | |
CN113337085A (en) | Modified starch-based PBAT biodegradable film material and preparation method thereof | |
CN112375354A (en) | Carbon fiber polylactic acid filling master batch and preparation method thereof | |
CN109880325A (en) | A kind of degradable new polyester composite material and preparation method |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210309 |
|
RJ01 | Rejection of invention patent application after publication |