CN112724626A - Degradable biological film and preparation method thereof - Google Patents
Degradable biological film and preparation method thereof Download PDFInfo
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- CN112724626A CN112724626A CN202110175483.9A CN202110175483A CN112724626A CN 112724626 A CN112724626 A CN 112724626A CN 202110175483 A CN202110175483 A CN 202110175483A CN 112724626 A CN112724626 A CN 112724626A
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- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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- C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
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Abstract
The invention is suitable for the technical field of films, and provides a degradable biological film and a preparation method thereof, wherein the degradable biological film comprises the following components: polylactic acid, chitosan, formamidine sulfinic acid, carboxymethyl cellulose, a plasticizer, a filling material and a coupling agent. According to the embodiment of the invention, the polylactic acid can be subjected to compound modification by adding chitosan, formamidine sulfinic acid and carboxymethyl cellulose, so that the toughness and the degradation speed of the degradable biological film are improved. The sulfonic group of the formamidine sulfinic acid and the carboxyl group of the carboxymethyl cellulose can react with the amino group of the chitosan, and the formamidine sulfinic acid can be heated and decomposed at high temperature, so that the chitosan can be better combined with polylactic acid, and a flexible chain is introduced, thereby the toughness and the degradation speed of the degradable biological film can be obviously improved.
Description
Technical Field
The invention belongs to the technical field of films, and particularly relates to a degradable biological film and a preparation method thereof.
Background
The degradable biological film is a film which can be split and degraded in natural environment by the action of microorganisms in soil and water or by the action of ultraviolet rays in sunlight.
Wherein, the polylactic acid is a biodegradable polymer material with renewable raw materials. Polylactic acid is widely used as a material for a degradable bio-film because of its excellent biocompatibility and biodegradability. However, the existing polylactic acid degradable biological film has the problems of poor mechanical properties such as toughness and the like, slow degradation speed and the like.
Disclosure of Invention
An object of an embodiment of the present invention is to provide a degradable biofilm, which aims to solve the problems in the background art.
The embodiment of the invention is realized in such a way that the degradable biological film comprises the following components in parts by weight: 800-1200 parts of polylactic acid, 50-200 parts of chitosan, 10-100 parts of formamidine sulfinic acid, 10-100 parts of carboxymethyl cellulose, 50-200 parts of plasticizer, 50-200 parts of filler and 10-100 parts of coupling agent.
As a preferable scheme of the embodiment of the invention, the degradable biological film comprises the following components in parts by weight: 900-1100 parts of polylactic acid, 100-150 parts of chitosan, 40-60 parts of formamidine sulfinic acid, 40-60 parts of carboxymethyl cellulose, 100-150 parts of plasticizer, 100-150 parts of filler and 40-60 parts of coupling agent.
As another preferable aspect of the embodiment of the present invention, the plasticizer is polyethylene glycol and/or tributyl citrate.
As another preferable scheme of the embodiment of the present invention, the filler is at least one of nano silica, nano titanium dioxide and calcium carbonate.
In another preferred embodiment of the present invention, the coupling agent is at least one of vinyltrimethoxysilane, vinyltriethoxysilane and octamethylcyclotetrasiloxane.
Another object of an embodiment of the present invention is to provide a method for preparing the above degradable biofilm, which comprises the following steps:
weighing polylactic acid, chitosan, formamidine sulfinic acid, carboxymethyl cellulose, a plasticizer, a filling material and a coupling agent according to the weight parts of the components;
mixing formamidine sulfinic acid, carboxymethyl cellulose and water to obtain a mixed solution;
mixing chitosan with the mixed solution to obtain a modified solution;
adding polylactic acid into the modified solution for modification treatment, filtering, and heating at 130-150 ℃ to obtain modified polylactic acid;
and mixing the modified polylactic acid with a plasticizer, a filling material and a coupling agent, and then carrying out extrusion blow molding treatment to obtain the degradable biological film.
In another preferable scheme of the embodiment of the invention, in the step, the temperature of the extrusion blow molding treatment is 180-200 ℃.
In another preferable scheme of the embodiment of the invention, in the step, the mixing temperature of the formamidine sulfinic acid, the carboxymethyl cellulose and the water is 60-80 ℃.
In another preferable embodiment of the invention, in the step, the mass of the water is 10 to 100 times of the sum of the mass of the formamidine sulfinic acid and the mass of the carboxymethyl cellulose.
Another object of the embodiments of the present invention is to provide a degradable biofilm prepared by the above preparation method.
According to the degradable biological film provided by the embodiment of the invention, the polylactic acid can be subjected to compound modification by adding the chitosan, the formamidine sulfinic acid and the carboxymethyl cellulose, so that the toughness and the degradation speed of the degradable biological film are improved. The sulfonic group of the formamidine sulfinic acid and the carboxyl group of the carboxymethyl cellulose can react with the amino group of the chitosan, and the formamidine sulfinic acid can be heated and decomposed at high temperature, so that the chitosan can be better combined with polylactic acid, and a flexible chain is introduced, thereby the toughness and the degradation speed of the degradable biological film can be obviously improved.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to 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 1
This embodiment provides a degradable biofilm, the preparation method of which comprises the steps of:
s1, weighing 800g of polylactic acid, 50g of chitosan, 10g of formamidine sulfinic acid, 10g of carboxymethyl cellulose, 50g of plasticizer, 200g of filler and 10g of coupling agent for later use; wherein the plasticizer is a mixture of polyethylene glycol and tributyl citrate in equal mass ratio; the filling material is a mixture of nano silicon dioxide, nano titanium dioxide and calcium carbonate in equal mass ratio; the coupling agent is a mixture of vinyltrimethoxysilane, vinyltriethoxysilane and octamethylcyclotetrasiloxane in equal mass ratio.
S2, placing the weighed formamidine sulfinic acid, carboxymethyl cellulose and 2000g of water at the temperature of 60 ℃ for fully mixing to obtain a mixed solution.
And S3, fully and uniformly mixing the weighed chitosan and the mixed solution to obtain a modified solution.
S4, adding the weighed polylactic acid into the modified solution, carrying out modification treatment for 30min at the stirring speed of 500rpm, filtering, and then heating at the temperature of 130 ℃ to obtain the modified polylactic acid.
And S5, mixing the obtained modified polylactic acid with the weighed plasticizer, filler and coupling agent, and then placing the mixture in a single-screw extrusion blow molding machine with the temperature set to be 180-200 ℃ for extrusion blow molding treatment to obtain the degradable biological film.
Example 2
This embodiment provides a degradable biofilm, the preparation method of which comprises the steps of:
s1, weighing 1200g of polylactic acid, 200g of chitosan, 100g of formamidine sulfinic acid, 100g of carboxymethyl cellulose, 200g of plasticizer, 50g of filler and 100g of coupling agent for later use; wherein the plasticizer is polyethylene glycol; the filling material is nano silicon dioxide; the coupling agent is a mixture of vinyl trimethoxy silane and octamethylcyclotetrasiloxane in equal mass ratio.
S2, placing the weighed formamidine sulfinic acid, carboxymethyl cellulose and 2000g of water at the temperature of 80 ℃ for fully mixing to obtain a mixed solution.
And S3, fully and uniformly mixing the weighed chitosan and the mixed solution to obtain a modified solution.
S4, adding the weighed polylactic acid into the modified solution, carrying out modification treatment for 1h at the stirring speed of 800rpm, filtering, and then heating at the temperature of 150 ℃ to obtain the modified polylactic acid.
And S5, mixing the obtained modified polylactic acid with the weighed plasticizer, filler and coupling agent, and then placing the mixture in a single-screw extrusion blow molding machine with the temperature set to be 180-200 ℃ for extrusion blow molding treatment to obtain the degradable biological film.
Example 3
This embodiment provides a degradable biofilm, the preparation method of which comprises the steps of:
s1, weighing 850g of polylactic acid, 180g of chitosan, 20g of formamidine sulfinic acid, 90g of carboxymethyl cellulose, 60g of plasticizer, 60g of filler and 20g of coupling agent for later use; wherein the plasticizer is tributyl citrate; the filling material is a mixture of nano titanium dioxide and calcium carbonate in equal mass ratio; the coupling agent is octamethylcyclotetrasiloxane.
S2, placing the weighed formamidine sulfinic acid, carboxymethyl cellulose and 2000g of water at the temperature of 65 ℃ for fully mixing to obtain a mixed solution.
And S3, fully and uniformly mixing the weighed chitosan and the mixed solution to obtain a modified solution.
S4, adding the weighed polylactic acid into the modified solution, carrying out modification treatment for 45min at a stirring speed of 600rpm, filtering, and then heating at 135 ℃ to obtain the modified polylactic acid.
And S5, mixing the modified polylactic acid with the plasticizer, the filling material and the coupling agent, and then placing the mixture in a single-screw extrusion blow molding machine with the temperature set to 185 ℃ for extrusion blow molding treatment to obtain the degradable biological film.
Example 4
This embodiment provides a degradable biofilm, the preparation method of which comprises the steps of:
s1, weighing 1050g of polylactic acid, 60g of chitosan, 90g of formamidine sulfinic acid, 20g of carboxymethyl cellulose, 180g of plasticizer, 180g of filler and 80g of coupling agent for later use; wherein the plasticizer is a mixture of polyethylene glycol and tributyl citrate in equal mass ratio; the filling material is nano titanium dioxide; the coupling agent is vinyl triethoxysilane.
S2, placing the weighed formamidine sulfinic acid, carboxymethyl cellulose and 2000g of water at 75 ℃ for fully mixing to obtain a mixed solution.
And S3, fully and uniformly mixing the weighed chitosan and the mixed solution to obtain a modified solution.
S4, adding the weighed polylactic acid into the modified solution, carrying out modification treatment for 1h at a stirring speed of 750rpm, filtering, and then heating at 145 ℃ to obtain the modified polylactic acid.
And S5, mixing the modified polylactic acid with the plasticizer, the filling material and the coupling agent, and then placing the mixture into a single-screw extrusion blow molding machine with the temperature set at 195 ℃ for extrusion blow molding treatment to obtain the degradable biological film.
Example 5
This embodiment provides a degradable biofilm, the preparation method of which comprises the steps of:
s1, weighing 900g of polylactic acid, 100g of chitosan, 40g of formamidine sulfinic acid, 40g of carboxymethyl cellulose, 100g of plasticizer, 150g of filler and 40g of coupling agent for later use; wherein the plasticizer is a mixture of polyethylene glycol and tributyl citrate in equal mass ratio; the filling material is nano silicon dioxide; the coupling agent is vinyl trimethoxy silane.
S2, placing the weighed formamidine sulfinic acid, carboxymethyl cellulose and 2000g of water at 70 ℃ for fully mixing to obtain a mixed solution.
And S3, fully and uniformly mixing the weighed chitosan and the mixed solution to obtain a modified solution.
S4, adding the weighed polylactic acid into the modified solution, carrying out modification treatment for 1h at the stirring speed of 700rpm, filtering, and then heating at the temperature of 140 ℃ to obtain the modified polylactic acid.
And S5, mixing the modified polylactic acid with the weighed plasticizer, filler and coupling agent, and then placing the mixture in a single-screw extrusion blow molding machine with the temperature set at 190 ℃ for extrusion blow molding treatment to obtain the degradable biological film.
Example 6
This embodiment provides a degradable biofilm, the preparation method of which comprises the steps of:
s1, weighing 1100g of polylactic acid, 150g of chitosan, 60g of formamidine sulfinic acid, 60g of carboxymethyl cellulose, 150g of plasticizer, 100g of filler and 60g of coupling agent for later use; wherein the plasticizer is a mixture of polyethylene glycol and tributyl citrate in equal mass ratio; the filling material is nano silicon dioxide; the coupling agent is vinyl trimethoxy silane.
S2, placing the weighed formamidine sulfinic acid, carboxymethyl cellulose and 2000g of water at 70 ℃ for fully mixing to obtain a mixed solution.
And S3, fully and uniformly mixing the weighed chitosan and the mixed solution to obtain a modified solution.
S4, adding the weighed polylactic acid into the modified solution, carrying out modification treatment for 1h at the stirring speed of 700rpm, filtering, and then heating at the temperature of 140 ℃ to obtain the modified polylactic acid.
And S5, mixing the modified polylactic acid with the weighed plasticizer, filler and coupling agent, and then placing the mixture in a single-screw extrusion blow molding machine with the temperature set at 190 ℃ for extrusion blow molding treatment to obtain the degradable biological film.
Example 7
This embodiment provides a degradable biofilm, the preparation method of which comprises the steps of:
s1, weighing 950g of polylactic acid, 120g of chitosan, 45g of formamidine sulfinic acid, 55g of carboxymethyl cellulose, 105g of plasticizer, 115g of filler and 45g of coupling agent for later use; wherein the plasticizer is a mixture of polyethylene glycol and tributyl citrate in equal mass ratio; the filling material is nano silicon dioxide; the coupling agent is vinyl trimethoxy silane.
S2, placing the weighed formamidine sulfinic acid, carboxymethyl cellulose and 2000g of water at 70 ℃ for fully mixing to obtain a mixed solution.
And S3, fully and uniformly mixing the weighed chitosan and the mixed solution to obtain a modified solution.
S4, adding the weighed polylactic acid into the modified solution, carrying out modification treatment for 1h at the stirring speed of 700rpm, filtering, and then heating at the temperature of 140 ℃ to obtain the modified polylactic acid.
And S5, mixing the modified polylactic acid with the weighed plasticizer, filler and coupling agent, and then placing the mixture in a single-screw extrusion blow molding machine with the temperature set at 190 ℃ for extrusion blow molding treatment to obtain the degradable biological film.
Example 8
This embodiment provides a degradable biofilm, the preparation method of which comprises the steps of:
s1, weighing 1050g of polylactic acid, 140g of chitosan, 60g of formamidine sulfinic acid, 40g of carboxymethyl cellulose, 140g of plasticizer, 110g of filler and 55g of coupling agent for later use; wherein the plasticizer is a mixture of polyethylene glycol and tributyl citrate in equal mass ratio; the filling material is nano silicon dioxide; the coupling agent is vinyl trimethoxy silane.
S2, placing the weighed formamidine sulfinic acid, carboxymethyl cellulose and 2000g of water at 70 ℃ for fully mixing to obtain a mixed solution.
And S3, fully and uniformly mixing the weighed chitosan and the mixed solution to obtain a modified solution.
S4, adding the weighed polylactic acid into the modified solution, carrying out modification treatment for 1h at the stirring speed of 700rpm, filtering, and then heating at the temperature of 140 ℃ to obtain the modified polylactic acid.
And S5, mixing the modified polylactic acid with the weighed plasticizer, filler and coupling agent, and then placing the mixture in a single-screw extrusion blow molding machine with the temperature set at 190 ℃ for extrusion blow molding treatment to obtain the degradable biological film.
Example 9
This embodiment provides a degradable biofilm, the preparation method of which comprises the steps of:
s1, weighing 920g of polylactic acid, 120g of chitosan, 48g of formamidine sulfinic acid, 42g of carboxymethyl cellulose, 130g of plasticizer, 120g of filler and 50g of coupling agent for later use; wherein the plasticizer is a mixture of polyethylene glycol and tributyl citrate in equal mass ratio; the filling material is nano silicon dioxide; the coupling agent is vinyl trimethoxy silane.
S2, placing the weighed formamidine sulfinic acid, carboxymethyl cellulose and 2000g of water at 70 ℃ for fully mixing to obtain a mixed solution.
And S3, fully and uniformly mixing the weighed chitosan and the mixed solution to obtain a modified solution.
S4, adding the weighed polylactic acid into the modified solution, carrying out modification treatment for 1h at the stirring speed of 700rpm, filtering, and then heating at the temperature of 140 ℃ to obtain the modified polylactic acid.
And S5, mixing the modified polylactic acid with the weighed plasticizer, filler and coupling agent, and then placing the mixture in a single-screw extrusion blow molding machine with the temperature set at 190 ℃ for extrusion blow molding treatment to obtain the degradable biological film.
Example 10
This embodiment provides a degradable biofilm, the preparation method of which comprises the steps of:
s1, weighing 1000g of polylactic acid, 100g of chitosan, 50g of formamidine sulfinic acid, 50g of carboxymethyl cellulose, 1000g of plasticizer, 100g of filler and 50g of coupling agent for later use; wherein the plasticizer is a mixture of polyethylene glycol and tributyl citrate in equal mass ratio; the filling material is nano silicon dioxide; the coupling agent is vinyl trimethoxy silane.
S2, placing the weighed formamidine sulfinic acid, carboxymethyl cellulose and 2000g of water at 70 ℃ for fully mixing to obtain a mixed solution.
And S3, fully and uniformly mixing the weighed chitosan and the mixed solution to obtain a modified solution.
S4, adding the weighed polylactic acid into the modified solution, carrying out modification treatment for 1h at the stirring speed of 700rpm, filtering, and then heating at the temperature of 140 ℃ to obtain the modified polylactic acid.
And S5, mixing the modified polylactic acid with the weighed plasticizer, filler and coupling agent, and then placing the mixture in a single-screw extrusion blow molding machine with the temperature set at 190 ℃ for extrusion blow molding treatment to obtain the degradable biological film.
Example 11
This embodiment provides a degradable biofilm, the preparation method of which comprises the steps of:
s1, weighing 1000g of polylactic acid, 150g of chitosan, 60g of formamidine sulfinic acid, 50g of carboxymethyl cellulose, 140g of plasticizer, 110g of filler and 50g of coupling agent for later use; wherein the plasticizer is a mixture of polyethylene glycol and tributyl citrate in equal mass ratio; the filling material is nano silicon dioxide; the coupling agent is vinyl trimethoxy silane.
S2, placing the weighed formamidine sulfinic acid, carboxymethyl cellulose and 2000g of water at 70 ℃ for fully mixing to obtain a mixed solution.
And S3, fully and uniformly mixing the weighed chitosan and the mixed solution to obtain a modified solution.
S4, adding the weighed polylactic acid into the modified solution, carrying out modification treatment for 1h at the stirring speed of 700rpm, filtering, and then heating at the temperature of 140 ℃ to obtain the modified polylactic acid.
And S5, mixing the modified polylactic acid with the weighed plasticizer, filler and coupling agent, and then placing the mixture in a single-screw extrusion blow molding machine with the temperature set at 190 ℃ for extrusion blow molding treatment to obtain the degradable biological film.
Example 12
This embodiment provides a degradable biofilm, the preparation method of which comprises the steps of:
s1, weighing 980g of polylactic acid, 120g of chitosan, 50g of formamidine sulfinic acid, 50g of carboxymethyl cellulose, 110g of plasticizer, 140g of filler and 50g of coupling agent for later use; wherein the plasticizer is a mixture of polyethylene glycol and tributyl citrate in equal mass ratio; the filling material is nano silicon dioxide; the coupling agent is vinyl trimethoxy silane.
S2, placing the weighed formamidine sulfinic acid, carboxymethyl cellulose and 2000g of water at 70 ℃ for fully mixing to obtain a mixed solution.
And S3, fully and uniformly mixing the weighed chitosan and the mixed solution to obtain a modified solution.
S4, adding the weighed polylactic acid into the modified solution, carrying out modification treatment for 1h at the stirring speed of 700rpm, filtering, and then heating at the temperature of 140 ℃ to obtain the modified polylactic acid.
And S5, mixing the modified polylactic acid with the weighed plasticizer, filler and coupling agent, and then placing the mixture in a single-screw extrusion blow molding machine with the temperature set at 190 ℃ for extrusion blow molding treatment to obtain the degradable biological film.
Example 13
This embodiment provides a degradable biofilm, the preparation method of which comprises the steps of:
s1, weighing 1020g of polylactic acid, 130g of chitosan, 40g of formamidine sulfinic acid, 60g of carboxymethyl cellulose, 150g of plasticizer, 150g of filler and 50g of coupling agent for later use; wherein the plasticizer is a mixture of polyethylene glycol and tributyl citrate in equal mass ratio; the filling material is nano silicon dioxide; the coupling agent is vinyl trimethoxy silane.
S2, placing the weighed formamidine sulfinic acid, carboxymethyl cellulose and 2000g of water at 70 ℃ for fully mixing to obtain a mixed solution.
And S3, fully and uniformly mixing the weighed chitosan and the mixed solution to obtain a modified solution.
S4, adding the weighed polylactic acid into the modified solution, carrying out modification treatment for 1h at the stirring speed of 700rpm, filtering, and then heating at the temperature of 140 ℃ to obtain the modified polylactic acid.
And S5, mixing the modified polylactic acid with the weighed plasticizer, filler and coupling agent, and then placing the mixture in a single-screw extrusion blow molding machine with the temperature set at 190 ℃ for extrusion blow molding treatment to obtain the degradable biological film.
Example 14
This embodiment provides a degradable biofilm, the preparation method of which comprises the steps of:
s1, weighing 1080g of polylactic acid, 120g of chitosan, 55g of formamidine sulfinic acid, 45g of carboxymethyl cellulose, 125g of plasticizer, 125g of filler and 50g of coupling agent for later use; wherein the plasticizer is a mixture of polyethylene glycol and tributyl citrate in equal mass ratio; the filling material is nano silicon dioxide; the coupling agent is vinyl trimethoxy silane.
S2, placing the weighed formamidine sulfinic acid, carboxymethyl cellulose and 2000g of water at 70 ℃ for fully mixing to obtain a mixed solution.
And S3, fully and uniformly mixing the weighed chitosan and the mixed solution to obtain a modified solution.
S4, adding the weighed polylactic acid into the modified solution, carrying out modification treatment for 1h at the stirring speed of 700rpm, filtering, and then heating at the temperature of 140 ℃ to obtain the modified polylactic acid.
And S5, mixing the modified polylactic acid with the weighed plasticizer, filler and coupling agent, and then placing the mixture in a single-screw extrusion blow molding machine with the temperature set at 190 ℃ for extrusion blow molding treatment to obtain the degradable biological film.
Example 15
This embodiment provides a degradable biofilm, the preparation method of which comprises the steps of:
s1, weighing 1000g of polylactic acid, 125g of chitosan, 50g of formamidine sulfinic acid, 50g of carboxymethyl cellulose, 125g of plasticizer, 125g of filler and 50g of coupling agent for later use; wherein the plasticizer is a mixture of polyethylene glycol and tributyl citrate in equal mass ratio; the filling material is nano silicon dioxide; the coupling agent is vinyl trimethoxy silane.
S2, placing the weighed formamidine sulfinic acid, carboxymethyl cellulose and 2000g of water at 70 ℃ for fully mixing to obtain a mixed solution.
And S3, fully and uniformly mixing the weighed chitosan and the mixed solution to obtain a modified solution.
S4, adding the weighed polylactic acid into the modified solution, carrying out modification treatment for 1h at the stirring speed of 700rpm, filtering, and then heating at the temperature of 140 ℃ to obtain the modified polylactic acid.
And S5, mixing the modified polylactic acid with the weighed plasticizer, filler and coupling agent, and then placing the mixture in a single-screw extrusion blow molding machine with the temperature set at 190 ℃ for extrusion blow molding treatment to obtain the degradable biological film.
Comparative example 1 (lack of formamidine sulfinic acid component compared to example 15)
The comparative example provides a degradable biofilm, and the preparation method thereof comprises the following steps:
s1, weighing 1000g of polylactic acid, 125g of chitosan, 100g of carboxymethyl cellulose, 125g of plasticizer, 125g of filler and 50g of coupling agent for later use; wherein the plasticizer is a mixture of polyethylene glycol and tributyl citrate in equal mass ratio; the filling material is nano silicon dioxide; the coupling agent is vinyl trimethoxy silane.
S2, placing the weighed carboxymethyl cellulose and 2000g of water at 70 ℃ for fully mixing to obtain a mixed solution.
And S3, fully and uniformly mixing the weighed chitosan and the mixed solution to obtain a modified solution.
S4, adding the weighed polylactic acid into the modified solution, carrying out modification treatment for 1h at the stirring speed of 700rpm, filtering, and then heating at the temperature of 140 ℃ to obtain the modified polylactic acid.
And S5, mixing the modified polylactic acid with the weighed plasticizer, filler and coupling agent, and then placing the mixture in a single-screw extrusion blow molding machine with the temperature set at 190 ℃ for extrusion blow molding treatment to obtain the degradable biological film.
Comparative example 2 (lack of carboxymethyl cellulose component compared to example 15)
The comparative example provides a degradable biofilm, and the preparation method thereof comprises the following steps:
s1, weighing 1000g of polylactic acid, 125g of chitosan, 100g of formamidine sulfinic acid, 125g of plasticizer, 125g of filler and 50g of coupling agent for later use; wherein the plasticizer is a mixture of polyethylene glycol and tributyl citrate in equal mass ratio; the filling material is nano silicon dioxide; the coupling agent is vinyl trimethoxy silane.
S2, placing the weighed formamidine sulfinic acid and 2000g of water at 70 ℃ for fully mixing to obtain a mixed solution.
And S3, fully and uniformly mixing the weighed chitosan and the mixed solution to obtain a modified solution.
S4, adding the weighed polylactic acid into the modified solution, carrying out modification treatment for 1h at the stirring speed of 700rpm, filtering, and then heating at the temperature of 140 ℃ to obtain the modified polylactic acid.
And S5, mixing the modified polylactic acid with the weighed plasticizer, filler and coupling agent, and then placing the mixture in a single-screw extrusion blow molding machine with the temperature set at 190 ℃ for extrusion blow molding treatment to obtain the degradable biological film.
Comparative example 3 (lack of Chitosan component compared to example 15)
The comparative example provides a degradable biofilm, and the preparation method thereof comprises the following steps:
s1, weighing 1125g of polylactic acid, 50g of formamidine sulfinic acid, 50g of carboxymethyl cellulose, 125g of plasticizer, 125g of filler and 50g of coupling agent for later use; wherein the plasticizer is a mixture of polyethylene glycol and tributyl citrate in equal mass ratio; the filling material is nano silicon dioxide; the coupling agent is vinyl trimethoxy silane.
S2, placing the weighed formamidine sulfinic acid, carboxymethyl cellulose and 2000g of water at 70 ℃ for fully mixing to obtain a mixed solution.
S3, adding the weighed polylactic acid into the mixed solution, carrying out modification treatment for 1h at the stirring speed of 700rpm, filtering, and then heating at the temperature of 140 ℃ to obtain the modified polylactic acid.
And S4, mixing the modified polylactic acid with the weighed plasticizer, filler and coupling agent, and then placing the mixture in a single-screw extrusion blow molding machine with the temperature set at 190 ℃ for extrusion blow molding treatment to obtain the degradable biological film.
Comparative example 4 (lack of formamidine sulfinic acid and carboxymethyl cellulose component compared to example 15)
The comparative example provides a degradable biofilm, and the preparation method thereof comprises the following steps:
s1, weighing 1100g of polylactic acid, 125g of chitosan, 125g of plasticizer, 125g of filler and 50g of coupling agent for later use; wherein the plasticizer is a mixture of polyethylene glycol and tributyl citrate in equal mass ratio; the filling material is nano silicon dioxide; the coupling agent is vinyl trimethoxy silane.
S2, fully and uniformly mixing the weighed chitosan and water to obtain a modified solution.
S3, adding the weighed polylactic acid into the modified solution, carrying out modification treatment for 1h at the stirring speed of 700rpm, filtering, and then heating at the temperature of 140 ℃ to obtain the modified polylactic acid.
And S4, mixing the modified polylactic acid with the weighed plasticizer, filler and coupling agent, and then placing the mixture in a single-screw extrusion blow molding machine with the temperature set at 190 ℃ for extrusion blow molding treatment to obtain the degradable biological film.
Comparative example 5 (lack of Chitosan, formamidine sulfinic acid, carboxymethyl cellulose component compared to example 15)
The comparative example provides a degradable biofilm, and the preparation method thereof comprises the following steps:
s1, weighing 1225g of polylactic acid, 125g of plasticizer, 125g of filler and 50g of coupling agent for later use; wherein the plasticizer is a mixture of polyethylene glycol and tributyl citrate in equal mass ratio; the filling material is nano silicon dioxide; the coupling agent is vinyl trimethoxy silane.
S2, mixing the weighed polylactic acid with a plasticizer, a filling material and a coupling agent, and then placing the mixture in a single-screw extrusion blow molding machine with the temperature set at 190 ℃ for extrusion blow molding treatment to obtain the degradable biological film.
Comparative example 6 (preparation method is different compared to example 15)
The comparative example provides a degradable biofilm, and the preparation method thereof comprises the following steps:
s1, weighing 1000g of polylactic acid, 125g of chitosan, 50g of formamidine sulfinic acid, 50g of carboxymethyl cellulose, 125g of plasticizer, 125g of filler and 50g of coupling agent for later use; wherein the plasticizer is a mixture of polyethylene glycol and tributyl citrate in equal mass ratio; the filling material is nano silicon dioxide; the coupling agent is vinyl trimethoxy silane.
S2, mixing the weighed formamidine sulfinic acid, carboxymethyl cellulose, chitosan, polylactic acid, plasticizer, filler and coupling agent, and then placing the mixture in a single-screw extrusion blow molding machine with the temperature set at 190 ℃ for extrusion blow molding treatment to obtain the degradable biological film.
Experimental example:
first, the tensile strength and elongation at break of the degradable biofilms prepared in the above examples 11 to 15 and comparative examples 1 to 6 were respectively tested according to the standard GB/T1040.1 to 2018, and the results are shown in table 1.
Secondly, the degradation days required for the degradation rate of the degradable biological films prepared in the above examples 11-15 and comparative examples 1-6 to reach more than 95% are respectively tested according to the standard GB/T20197-2006, and the results are shown in Table 1.
TABLE 1
As can be seen from Table 1, in the embodiment of the invention, the polylactic acid can be modified by adding chitosan, formamidine sulfinic acid and carboxymethyl cellulose, so as to improve the toughness and degradation speed of the degradable biofilm. The sulfonic group of the formamidine sulfinic acid and the carboxyl group of the carboxymethyl cellulose added in the embodiment of the invention can react with the amino group of the chitosan, and the formamidine sulfinic acid can be decomposed by heating at high temperature, so that the chitosan can be better combined with polylactic acid, and a flexible chain is introduced, thereby obviously improving the toughness and the degradation speed of the degradable biofilm.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (10)
1. The degradable biological film is characterized by comprising the following components in parts by weight: 800-1200 parts of polylactic acid, 50-200 parts of chitosan, 10-100 parts of formamidine sulfinic acid, 10-100 parts of carboxymethyl cellulose, 50-200 parts of plasticizer, 50-200 parts of filler and 10-100 parts of coupling agent.
2. The degradable biofilm according to claim 1, wherein said degradable biofilm comprises the following components in parts by weight: 900-1100 parts of polylactic acid, 100-150 parts of chitosan, 40-60 parts of formamidine sulfinic acid, 40-60 parts of carboxymethyl cellulose, 100-150 parts of plasticizer, 100-150 parts of filler and 40-60 parts of coupling agent.
3. The degradable biofilm according to claim 1 or 2, wherein said plasticizer is polyethylene glycol and/or tributyl citrate.
4. The degradable biofilm according to claim 1 or 2, wherein said filler is at least one of nano silica, nano titania and calcium carbonate.
5. The degradable biofilm according to claim 1 or 2, wherein said coupling agent is at least one of vinyltrimethoxysilane, vinyltriethoxysilane, and octamethylcyclotetrasiloxane.
6. A method for preparing a degradable biofilm according to any one of claims 1 to 5, comprising the following steps:
weighing polylactic acid, chitosan, formamidine sulfinic acid, carboxymethyl cellulose, a plasticizer, a filling material and a coupling agent according to the weight parts of the components;
mixing formamidine sulfinic acid, carboxymethyl cellulose and water to obtain a mixed solution;
mixing chitosan with the mixed solution to obtain a modified solution;
adding polylactic acid into the modified solution for modification treatment, filtering, and heating at 130-150 ℃ to obtain modified polylactic acid;
and mixing the modified polylactic acid with a plasticizer, a filling material and a coupling agent, and then carrying out extrusion blow molding treatment to obtain the degradable biological film.
7. The method for preparing a degradable biofilm according to claim 6, wherein the temperature of the extrusion blow molding treatment in the step is 180-200 ℃.
8. The method for preparing a degradable biofilm according to claim 6, wherein in the step, the mixing temperature of formamidine sulfinic acid, carboxymethyl cellulose and water is 60-80 ℃.
9. The method for preparing a degradable biofilm according to claim 6 or 8, wherein the mass of water in the step is 10-100 times of the sum of the mass of formamidine sulfinic acid and carboxymethyl cellulose.
10. A degradable biological film prepared by the preparation method of any one of claims 6 to 9.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113907071A (en) * | 2021-11-15 | 2022-01-11 | 扬州工业职业技术学院 | Degradable medicine slow-release material and preparation method thereof |
| CN115926478A (en) * | 2023-01-04 | 2023-04-07 | 陈时辉 | Composite degradable plastic and preparation method thereof |
| CN116925514A (en) * | 2023-09-15 | 2023-10-24 | 广州市奥鑫美塑胶有限公司 | Novel organic degradable material sheet and manufacturing method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019052150A1 (en) * | 2017-09-12 | 2019-03-21 | 江苏金聚合金材料有限公司 | Low-cost bio-based fully-degradable thin film and preparation method therefor |
| CN110016217A (en) * | 2019-04-30 | 2019-07-16 | 封金财 | A kind of preparation method of degradable agricultural composite plastic mulch |
| CN111500037A (en) * | 2020-06-03 | 2020-08-07 | 泉州陶纪塑胶有限公司 | High-density bamboo powder modified polylactic acid biodegradable plastic and preparation method thereof |
-
2021
- 2021-02-07 CN CN202110175483.9A patent/CN112724626A/en not_active Withdrawn
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019052150A1 (en) * | 2017-09-12 | 2019-03-21 | 江苏金聚合金材料有限公司 | Low-cost bio-based fully-degradable thin film and preparation method therefor |
| CN110016217A (en) * | 2019-04-30 | 2019-07-16 | 封金财 | A kind of preparation method of degradable agricultural composite plastic mulch |
| CN111500037A (en) * | 2020-06-03 | 2020-08-07 | 泉州陶纪塑胶有限公司 | High-density bamboo powder modified polylactic acid biodegradable plastic and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113907071A (en) * | 2021-11-15 | 2022-01-11 | 扬州工业职业技术学院 | Degradable medicine slow-release material and preparation method thereof |
| CN115926478A (en) * | 2023-01-04 | 2023-04-07 | 陈时辉 | Composite degradable plastic and preparation method thereof |
| CN116925514A (en) * | 2023-09-15 | 2023-10-24 | 广州市奥鑫美塑胶有限公司 | Novel organic degradable material sheet and manufacturing method thereof |
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