CN112796161A - Modified natural polymer and preparation method and application thereof - Google Patents
Modified natural polymer and preparation method and application thereof Download PDFInfo
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- CN112796161A CN112796161A CN202011628126.5A CN202011628126A CN112796161A CN 112796161 A CN112796161 A CN 112796161A CN 202011628126 A CN202011628126 A CN 202011628126A CN 112796161 A CN112796161 A CN 112796161A
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/50—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by form
- D21H21/52—Additives of definite length or shape
- D21H21/54—Additives of definite length or shape being spherical, e.g. microcapsules, beads
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
- D21H11/16—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only modified by a particular after-treatment
- D21H11/18—Highly hydrated, swollen or fibrillatable fibres
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
- D21H17/24—Polysaccharides
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
- D21H17/24—Polysaccharides
- D21H17/28—Starch
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
- D21H17/24—Polysaccharides
- D21H17/30—Alginic acid or alginates
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/71—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes
- D21H17/72—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes of organic material
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
Abstract
A carrier, a guanidine salt polymer, a plasticizer and a hydrophobic compound are mixed and stirred uniformly in sequence to obtain a mixture, the mixture is subjected to mixing melting, extrusion and granulation to obtain modified natural polymer particles, the rotating speed of a screw extruder is 150-180rpm, and the temperature of each temperature zone from a feed inlet to a discharge outlet is set. The paper-based antiviral material prepared by the invention has a good antiviral effect, has high density of antiviral effective functional groups, effectively avoids the problems of non-durable antiviral effect and pollution of other material substances caused by the loss of antiviral substances, and eliminates potential threats brought by leakage of the antiviral substances such as Ag and the like.
Description
Technical Field
The invention belongs to the technical field of antiviral materials, and particularly relates to a modified natural polymer and a preparation method and application thereof.
Background
Coronavirus (COVID-19), similar to influenza and SARS, belongs to a group of single-stranded positive-strand RNA viruses whose fat envelope is covered with a rod-shaped spike glycoprotein that drives the fusion of the virus with the host cell. Although coronaviruses can be destroyed with simple disinfectants, it remains a challenge to disinfect surfaces (e.g., paper packaging) for long-term effectiveness, and to avoid recontamination during shipping, etc. In this case, it is a more desirable solution to form a virucidal barrier on the surface of the material, which rapidly inactivates the virus upon contact, thereby eliminating viral transmission. Since paper products are closely related to our daily lives, the production of antiviral paper is one of the best ways to address consumer concerns.
The antiviral material has an antiviral effect mainly because an antiviral agent is contained in the material. Conventional antiviral agents are low molecular weight substances and thus cause leakage problems, and high molecular antiviral polymers are one of the important approaches to solve this problem. Alkyl or aryl substituted quaternary phosphonium salt type complex pair H3N2The virus has good antiviral activity. However, due to the complexity of the synthetic pathway, few reports have been made so far about its antiviral activity. It has been reported that pyridine-type polymers have a superior antiviral effect against influenza virus, a type of enveloped virus, which inactivates the virus by disrupting the viral outer lipid envelope.
However, there are few reports on antiviral paper in the market at present, and some existing products also face significant challenges. For example, antiviral tissues use citric acid as a key virucidal component, but its activity against COVID-19 virus is very low (30%); furthermore, the rapid release and leaching effect of antiviral nanoparticles (such as Ag) in paper products remains an unsolved problem.
Disclosure of Invention
The technical problem to be solved is as follows: the invention provides a modified natural polymer and a preparation method and application thereof, wherein the guanidyl polymer is modified to be suitable for preparing antiviral paper, and the obtained antiviral paper not only has an antiviral effect, but also has remarkable spectrum antibacterial performance, and does not damage human bodies.
The technical scheme is as follows: a process for preparing a modified natural polymer comprising the steps of: the preparation method comprises the following steps of sequentially mixing and stirring 40-60 parts by weight of carrier, namely starch, fine fiber, water-soluble fiber, chitosan or sodium alginate, 10-30 parts by weight of antiviral polymer, 5-25 parts by weight of plasticizer and 10-30 parts by weight of hydrophobic compound uniformly to obtain a mixture, carrying out mixing melting, extrusion and granulation on the mixture by using a ZSK18 mm MEGAlab screw extruder to obtain modified natural polymer particles, wherein the rotating speed of the screw extruder is 150-180rpm, and the temperature of each temperature zone from a feed inlet to a discharge outlet is 75-90 ℃/105 ℃ -130 ℃/135 ℃ -150 ℃/155 ℃/170 ℃ -180 ℃/160 ℃ -175 ℃/150 ℃ -170 ℃.
The starch is corn starch, potato starch, wheat starch or cassava starch, and the fine fiber is micro/nano-scale fiber obtained by mechanically or chemically treating wood base or grass base; the water-soluble fiber is carboxymethyl cellulose.
The antiviral polymer is: c12-C20The molecular weight of the hydrophobic modified macromolecule monoguanidine or biguanidine salt obtained by coupling the unsaturated long-chain fatty acid with the amino group of the guanidine salt polymer is 500-8000 before modification; the molecular weight after modification is 700-10000; the reaction molar ratio of the guanidinium group polymer to the long-chain fatty acid is 2-10; the guanidine-based polymer is polyhexamethylene guanidine hydrochloride or polyhexamethylene biguanide hydrochloride.
The plasticizer is a mixture of water and glycerol with a mass ratio of 0.5-5.
The hydrophobic compound is a fatty acid.
The preparation method of the modified natural polymer comprises the following steps of sequentially putting 45-60 parts by weight of a carrier, 15-30 parts by weight of a guanidinium polymer, 10-25 parts by weight of a plasticizer and 10-25 parts by weight of a hydrophobic compound into a feed inlet of an extruder; the rotating speed of the screw extruder is 155-170 rpm, and the temperature of each temperature zone of the double screw extruder from the feed inlet to the discharge outlet is 80-90 ℃/110-130 ℃/135-14 ℃/155-170 ℃/170-180 ℃/160-175 ℃/150-160 ℃ in sequence.
Modified natural polymers obtained by the above process.
The modified natural polymer is applied to preparing antiviral paper.
The application comprises the following specific steps: adding 0.1-10 wt.% of modified natural polymer particles based on dry paper pulp into the suspension of wood pulp or straw pulp for defibering, adding polyacrylamide accounting for 0.1-0.3 wt.% of the system, and papermaking on a paper pattern papermaking device to obtain the antiviral paper.
Preferably, 1wt.% to 20wt.% of aqueous solution of the modified natural polymer is directly coated on the surface of base paper by a papermaking surface sizing process or a coating machine to prepare a uniform antiviral thin layer, and the coating amount is 0.5 to 30g/m2。
Has the advantages that: the technical scheme of the invention provides a method for producing a paper-based antiviral material by modifying a natural polymer through a reactive extrusion method, wherein a carrier, an antiviral polymer, a plasticizer, a hydrophobic polymer and the like are mixed and processed through a screw extruder to prepare antiviral particles, and then the antiviral particles and the paper-based antiviral paper are prepared in a paper making or surface coating mode. In addition, the antiviral paper is environment-friendly paper, and can keep the degradability of the paper. The invention adopts modified guanidine salt of long-chain fatty acid and biguanide salt oligomer as an antiviral functional group, a hydrophobic chain can destroy a lipid envelope, guanidine salt is adsorbed on the surface of the lipid envelope through strong adsorption and is adhered on influenza virus, and then the lipid envelope is disordered and seriously destroyed due to the interaction with virus particles, so that the leakage of virus genome and the subsequent virus inactivation are caused. The fatty acid-modified guanidino has a good antiviral effect on genomic viruses, whether DNA or RNA, including viruses with an envelope such as influenza virus, herpes virus, varicella virus and non-enveloped viruses such as adenovirus, Coxsackie virus, etc. Therefore, the guanidine-based polymer of the grafted fatty acid is prepared by a reactive extrusion mode, and has deep significance for improving the antiviral performance of the product and widening the application range of the product.
Detailed Description
The invention is described in further detail below with reference to examples, but without limiting the scope of the invention as claimed, in which the following test methods are used:
and (3) determining the structure of the antiviral particles and the content of the monomer unit: determined by infrared spectroscopy, nuclear magnetism, and the like.
Microscopic morphology testing of antiviral particles: a transmission electron microscope;
mechanical properties of antiviral paper: tensile strength, tensile ratio, modulus of elasticity, tear index;
two representative classes of viruses: non-enveloped adenoviruses and enveloped influenza viruses;
the first step is as follows: reaction extrusion method antiviral particle production example
The mixture was fed into a twin-screw extruder, the detailed processing parameters being listed below:
equipment: a ZSK24 mm MEGAlab twin screw extruder (length-diameter ratio 35) was used for laboratory;
screw rotation speed: 150-;
temperature profile from feed port to die: 75 to 90/105 to 130/135 to 150/155 to 170/170 to 180/160 to 175/150 to 170 ℃;
melt temperature: 165-170 ℃;
mixing and stirring 5-25 parts by weight of plasticizer, 40-60 parts by weight of starch (one of corn, wheat, potato, cassava and the like) or fine fiber (carboxymethyl cellulose), 10-30 parts by weight of guanidine salt and fatty acid uniformly to obtain a mixture, mixing, melting, extruding and granulating the mixture to obtain natural antiviral particles, wherein the rotating speed of a screw extruder is 150-180rpm, and the temperature of each temperature zone from a feed inlet to a discharge outlet is 75-90/105-130/135-150/155-170/170-180/160-175/150-170 ℃; and cutting and granulating the product at the position of the extruder die directly through a granulator to finally obtain the antiviral granules.
The reaction molar ratio of the polyhexamethylene guanidine monohydrochloride or the biguanide hydrochloride to the long-chain fatty acid is 2-10, and the antiviral guanidine salt is obtained.
EXAMPLE 1 preparation of functionalized polyhexamethylene guanidine hydrochloride
20g of plasticizer, 45g of carrier, 15g of polyhexamethylene guanidine with guanidine salt molecular weight of 600 and 5g of 12 carbon fatty acid are mixed, melted, extruded and granulated in sequence by weight to obtain natural antiviral particles, the rotating speed of a screw extruder is 150rpm, and the temperature of each temperature zone from a feed inlet to a discharge outlet is 75/105/135/155/170/160/150 ℃;
EXAMPLE 2 preparation of functionalized polyhexamethyleneguanidine hydrochloride
The natural antiviral particle is prepared by mixing, melting, extruding and granulating 20g of plasticizer, 45g of carrier, 15g of polyhexamethylene guanidine hydrochloride with guanidine salt molecular weight of 600 and 15g of 16 carbon fatty acid in sequence by weight, wherein the rotating speed of a screw extruder is 150rpm, and the temperature of each temperature zone from a feed inlet to a discharge outlet is 75/105/135/155/170/160/150 ℃;
example 3 preparation of functionalized polyhexamethylene guanidine hydrochloride
20g of plasticizer, 45g of carrier, 15g of polyhexamethylene guanidine hydrochloride with guanidine salt molecular weight of 600 and 15g of 20 carbon fatty acid are mixed, melted, extruded and granulated in sequence by weight to obtain natural antiviral particles, the rotating speed of a screw extruder is 155rpm, and the temperature of each temperature zone from a feed inlet to a discharge outlet is 80/110/140/160/175/165/155 ℃;
example 4 preparation of functionalized polyhexamethyleneguanidine hydrochloride
The natural antiviral particle is prepared by mixing, melting, extruding and granulating 20g of plasticizer, 45g of carrier, 15g of polyhexamethylene guanidine hydrochloride with guanidine salt molecular weight of 1000 and 15g of 12 carbon fatty acid in sequence by weight, wherein the rotating speed of a screw extruder is 150rpm, and the temperature of each temperature zone from a feed inlet to a discharge outlet is 75/105/135/155/170/160/150 ℃;
EXAMPLE 5 preparation of functionalized polyhexamethyleneguanidine hydrochloride
The natural antiviral particle is prepared by mixing, melting, extruding and granulating 20g of plasticizer, 45g of carrier, 15g of polyhexamethylene guanidine hydrochloride with guanidine salt molecular weight of 1000 and 15g of 16 carbon fatty acid in sequence by weight, wherein the rotating speed of a screw extruder is 150rpm, and the temperature of each temperature zone from a feed inlet to a discharge outlet is 75/105/135/155/170/160/150 ℃;
EXAMPLE 6 preparation of functionalized polyhexamethyleneguanidine hydrochloride
The preparation method comprises the following steps of sequentially mixing, melting, extruding and granulating 20g of 45g of a carrier serving as a plasticizer, 15g of polyhexamethylene guanidine hydrochloride with guanidine salt molecular weight of 1000 and 15g of 20 carbon fatty acid in parts by weight to obtain natural antiviral particles, wherein the rotating speed of a screw extruder is 155rpm, and the temperature of each temperature zone from a feed inlet to a discharge outlet is 80/110/140/160/175/165/155 ℃;
example 7 preparation of functionalized polyhexamethylene guanidine hydrochloride
20g of plasticizer, 45g of carrier, 15g of polyhexamethylene guanidine hydrochloride with guanidine salt molecular weight of 1800 and 15g of 12 carbon fatty acid are mixed, melted, extruded and granulated in sequence by weight to obtain natural antiviral particles, the rotating speed of a screw extruder is 150rpm, and the temperature of each temperature zone from a feed inlet to a discharge outlet is 75/105/135/155/170/160/150 ℃;
EXAMPLE 8 preparation of functionalized polyhexamethyleneguanidine hydrochloride
20g of plasticizer, 45g of carrier, 15g of polyhexamethylene guanidine hydrochloride with guanidine salt molecular weight of 1800 and 215g of 16 carbon fatty acid are mixed, melted, extruded and granulated in sequence by weight to obtain natural antiviral particles, the rotating speed of a screw extruder is 150rpm, and the temperature of each temperature zone from a feed inlet to a discharge outlet is 75/105/135/155/170/160/150 ℃;
example 9 preparation of functionalized polyhexamethylene guanidine hydrochloride
20g of plasticizer, 45g of carrier, 15g of polyhexamethylene guanidine hydrochloride with guanidine salt molecular weight of 1800 and 15g of 20 carbon fatty acid are mixed, melted, extruded and granulated in sequence by weight to obtain natural antiviral particles, the rotating speed of a screw extruder is 155rpm, and the temperature of each temperature zone from a feed inlet to a discharge outlet is 80/110/140/160/175/165/155 ℃;
EXAMPLE 10 preparation of functionalized polyhexamethyleneguanidine hydrochloride
The preparation method comprises the following steps of sequentially mixing, melting, extruding and granulating 20g of plasticizer, 45g of carrier, 15g of polyhexamethylene guanidine hydrochloride with guanidine salt molecular weight of 4600 and 15g of 12 carbon fatty acid in parts by weight to obtain natural antiviral particles, wherein the rotating speed of a screw extruder is 150rpm, and the temperature of each temperature zone from a feed inlet to a discharge outlet is 75/105/135/155/170/160/150 ℃;
EXAMPLE 11 preparation of functionalized polyhexamethyleneguanidine hydrochloride
The preparation method comprises the following steps of sequentially mixing, melting, extruding and granulating 20g of plasticizer, 45g of carrier, 15g of polyhexamethylene guanidine hydrochloride with guanidine salt molecular weight of 4600 and 15g of 16 carbon fatty acid in parts by weight to obtain natural antiviral particles, wherein the rotating speed of a screw extruder is 150rpm, and the temperature of each temperature zone from a feed inlet to a discharge outlet is 75/105/135/155/170/160/150 ℃;
EXAMPLE 12 preparation of functionalized polyhexamethyleneguanidine hydrochloride
The natural antiviral particle is prepared by mixing, melting, extruding and granulating 20g of plasticizer, 45g of carrier, 15g of polyhexamethylene guanidine hydrochloride with guanidine salt molecular weight of 4600 and 15g of 20 carbon fatty acid in sequence by weight, wherein the rotating speed of a screw extruder is 155rpm, and the temperature of each temperature zone from a feed inlet to a discharge outlet is 80/110/140/160/175/165/155 ℃;
the second step is that: paper-based antiviral Material production examples
EXAMPLE 13 preparation of antiviral paper by in-pulp addition
The antiviral particles prepared in examples 1 to 12 (0.1 to 5% based on dry pulp) were added to a bleached kraft hardwood pulp suspension having a freeness of 35 ° SR concentration of 1%, the suspension was diluted to 0.5%, and then sheeted in a RK-2A type paper former (Frank-PTI GmhH, germany) according to ISO 5269/2 with a basis weight of 60g/m2. After drying, all samples were relativeAnd placing the mixture in a constant-temperature and constant-humidity chamber with the humidity of 52% and the temperature of 23-24 ℃ for 24h to balance the water.
Example 14 surface treatment preparation of antiviral paper
The antiviral particle solution (0-15 g/m) prepared in examples 1-122) The paper is coated on the paper without the added antiviral particles by a coating machine in a surface coating mode.
Application effect embodiment of antiviral paper manufactured in embodiment of the invention
Antiviral papers were prepared as in examples 13 and 14 using the antiviral particles of example 12 and antiviral tests were performed on two types of virus enveloped viruses and non-enveloped viruses, as follows:
the experiment was performed in 4 groups, test material group (test paper plus virus solution), blank paper (control paper plus virus solution), virus control group (containing only virus solution), and normal control group (containing only MEM culture solution). The test paper sample and the paper control sample were accurately weighed to 200mg each, and 3mL of virus solution was added. The four groups of samples are placed at room temperature for 30min at the same time, then centrifuged at 1000rpm for 10min at 4 ℃, and the supernatant is collected and placed in a refrigerator for later use.
Diluting the virus collection solution by 10 times, adding virus dilution solution with each concentration into 96-well cell culture plate of Vero cells, setting 4 wells for each dilution, 100 μ L/well and setting normal control group, adding equal amount of culture solution, placing at 37 deg.C and 5% CO2Is incubated in the incubator for 2 hours. After 2h, the supernatant was discarded, and the virus culture medium was added, followed by further culture for 2-4 days. The growth of the cells was observed daily and when Vero cells developed lesions (CPE) such as swelling, rounding and cell fusion, lesions were noted. Then 50% of the tissue cell infection amount (TCID) of the virus was calculated according to the Reed-Muench method50) The virus kill rate of the paper was calculated as follows:
the ratio of virus killing (%) - (A-B)/A100
A TCID of control pattern50(unit/mL); b TCID of an experiment paper pattern50(Unit/mL)
Table 1 shows the antiviral effects of antiviral papers prepared by adding different amounts of the antiviral particles prepared in example 12 by the in-pulp addition method on influenza virus and adenovirus; table 2 shows the antiviral effects of influenza virus and adenovirus on antiviral papers prepared by coating different amounts of the antiviral particles prepared in example 12 by surface processing
TABLE 1 antiviral Effect of paper sheets prepared by in-pulp addition method on influenza and adenovirus
TABLE 2 antiviral Effect of paper sheets prepared by surfacing on influenza and adenovirus
Researches show that the paper-based antiviral material prepared by the invention has good antiviral performance, and has a killing rate of more than 90% when the addition amount of antiviral particles is respectively 2% and 15% for both non-enveloped adenovirus and enveloped influenza virus. The foregoing is a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and variations can be made without departing from the technical principle of the invention, and these modifications and variations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A process for the preparation of a modified natural polymer, characterized in that it comprises the following steps: the preparation method comprises the following steps of sequentially mixing and stirring 40-60 parts by weight of carrier, namely starch, fine fiber, water-soluble fiber, chitosan or sodium alginate, 10-30 parts by weight of antiviral polymer, 5-25 parts by weight of plasticizer and 10-30 parts by weight of hydrophobic compound uniformly to obtain a mixture, carrying out mixing melting, extrusion and granulation on the mixture by using a ZSK18 mm MEGAlab screw extruder to obtain modified natural polymer particles, wherein the rotating speed of the screw extruder is 150-180rpm, and the temperature of each temperature zone from a feed inlet to a discharge outlet is 75-90 ℃/105 ℃ -130 ℃/135 ℃ -150 ℃/155 ℃/170 ℃ -180 ℃/160 ℃ -175 ℃/150 ℃ -170 ℃.
2. The process for the preparation of modified natural polymers according to claim 1, characterized in that the starch is corn, potato, wheat or tapioca starch, the fines are wood-or grass-based mechanically or chemically treated micro/nano-sized fibers; the water-soluble fiber is carboxymethyl cellulose.
3. The process for preparing a modified natural polymer according to claim 1, wherein the antiviral polymer is: c12-C20The molecular weight of the hydrophobic modified macromolecule monoguanidine or biguanidine salt obtained by coupling the unsaturated long-chain fatty acid with the amino group of the guanidine salt polymer is 500-8000 before modification; the molecular weight after modification is 700-10000; the reaction molar ratio of the guanidinium group polymer to the long-chain fatty acid is 2-10; the guanidine-based polymer is polyhexamethylene guanidine hydrochloride or polyhexamethylene biguanide hydrochloride.
4. The method for preparing a modified natural polymer according to claim 1, wherein the plasticizer is a mixture of water and glycerin in a mass ratio of 0.5 to 5.
5. The method for preparing a modified natural polymer according to claim 1, wherein the hydrophobic compound is a fatty acid.
6. The method for preparing the modified natural polymer according to claim 1, wherein 45 to 60 parts by weight of the carrier, 15 to 30 parts by weight of the guanidinium polymer, 10 to 25 parts by weight of the plasticizer and 10 to 25 parts by weight of the hydrophobic compound are sequentially fed into a feed port of an extruder; the rotating speed of the screw extruder is 155-170 rpm, and the temperature of each temperature zone of the double screw extruder from the feed inlet to the discharge outlet is 80-90 ℃/110-130 ℃/135-14 ℃/155-170 ℃/170-180 ℃/160-175 ℃/150-160 ℃ in sequence.
7. A modified natural polymer obtainable by the process of any one of claims 1 to 6.
8. Use of the modified natural polymer of claim 7 in the preparation of an antiviral paper.
9. The application of claim 8, characterized by the specific steps of: adding 0.1-10 wt.% of modified natural polymer particles based on dry paper pulp into the suspension of wood pulp or straw pulp for defibering, adding polyacrylamide accounting for 0.1-0.3 wt.% of the system, and papermaking on a paper pattern papermaking device to obtain the antiviral paper.
10. The application of claim 9, characterized by the specific steps of: directly coating 1-20 wt.% aqueous solution of modified natural polymer on the surface of base paper by using a papermaking surface sizing process or a coating machine to prepare a uniform antiviral thin layer, wherein the coating weight is 0.5-30g/m2。
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| CN104098831A (en) * | 2014-08-06 | 2014-10-15 | 南京神奇生物技术有限公司 | Migration-free antibiotic polyolefin film and preparation method thereof |
| CN108976768A (en) * | 2018-07-05 | 2018-12-11 | 中国科学院长春应用化学研究所 | Antibacterial modified dose a kind of and preparation method thereof, antibacterial modified thermoplastic elastomer (TPE) and preparation method thereof |
| CN109232998A (en) * | 2018-09-29 | 2019-01-18 | 南京林业大学 | A kind of chain SiO2Enhance the preparation method of thermoplastic starch plastic |
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2020
- 2020-12-31 CN CN202011628126.5A patent/CN112796161A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103497275A (en) * | 2013-08-09 | 2014-01-08 | 华北电力大学（保定） | Anti-bacterium antivirus guanidine salt star-shaped polymer, preparation method and applications thereof |
| CN103437247A (en) * | 2013-08-23 | 2013-12-11 | 华南理工大学 | Preparation method of paper with antibacterial effect |
| CN104098831A (en) * | 2014-08-06 | 2014-10-15 | 南京神奇生物技术有限公司 | Migration-free antibiotic polyolefin film and preparation method thereof |
| CN108976768A (en) * | 2018-07-05 | 2018-12-11 | 中国科学院长春应用化学研究所 | Antibacterial modified dose a kind of and preparation method thereof, antibacterial modified thermoplastic elastomer (TPE) and preparation method thereof |
| CN109232998A (en) * | 2018-09-29 | 2019-01-18 | 南京林业大学 | A kind of chain SiO2Enhance the preparation method of thermoplastic starch plastic |
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