CN113799514B - Environment-friendly paper file box with mould proof and insect prevention functions - Google Patents

Environment-friendly paper file box with mould proof and insect prevention functions Download PDF

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CN113799514B
CN113799514B CN202111121303.5A CN202111121303A CN113799514B CN 113799514 B CN113799514 B CN 113799514B CN 202111121303 A CN202111121303 A CN 202111121303A CN 113799514 B CN113799514 B CN 113799514B
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proof
mildew
insect
hyperbranched
nitrogen
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CN113799514A (en
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赵惠宇
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Guangzhou Pine Source Industrial Co ltd
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Guangzhou Pine Source Industrial Co ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
    • B42F—SHEETS TEMPORARILY ATTACHED TOGETHER; FILING APPLIANCES; FILE CARDS; INDEXING
    • B42F7/00—Filing appliances without fastening means
    • B42F7/14—Boxes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D81/00—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents
    • B65D81/24—Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants
    • B65D81/26—Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants with provision for draining away, or absorbing, or removing by ventilation, fluids, e.g. exuded by contents; Applications of corrosion inhibitors or desiccators
    • B65D81/263—Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants with provision for draining away, or absorbing, or removing by ventilation, fluids, e.g. exuded by contents; Applications of corrosion inhibitors or desiccators for ventilating the contents
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21F—PAPER-MAKING MACHINES; METHODS OF PRODUCING PAPER THEREON
    • D21F13/00—Making discontinuous sheets of paper, pulpboard or cardboard, or of wet web, for fibreboard production
    • D21F13/10—Making discontinuous sheets of paper, pulpboard or cardboard, or of wet web, for fibreboard production using board presses
    • 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
    • D21H21/36—Biocidal agents, e.g. fungicidal, bactericidal, insecticidal agents
    • 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
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes

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  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Food Science & Technology (AREA)
  • Mechanical Engineering (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The invention discloses an environment-friendly paper file box with mildew-proof and insect-proof functions, and belongs to the technical field of stationery. The file box comprises a box body, and both side surfaces of the box body are provided with vent holes; the box body is made of mildew-proof and insect-proof paperboard. The mildew-proof and insect-proof paperboard is prepared by adding hyperbranched quaternary phosphonium salt and compound essential oil into paper pulp, and utilizes the antibacterial property of the hyperbranched quaternary phosphonium salt and the insect expelling effect of the compound essential oil; the hyperbranched quaternary phosphonium salt has good water solubility, the molecular structure of the hyperbranched quaternary phosphonium salt contains a large number of hydrophobic cavities, the hydrophobic cavities can contain compound essential oil to promote the dissolving performance of the compound essential oil in paper pulp, and the hyperbranched quaternary phosphonium salt contains a large number of nitrogen and phosphorus elements to increase the flame retardant performance of the paper board; therefore, the file box has mildew-proof, insect-proof and flame-retardant properties.

Description

Environment-friendly paper file box with mould proof and insect prevention functions
Technical Field
The invention belongs to the technical field of stationery, and particularly relates to an environment-friendly paper file box with mildew-proof and insect-proof functions.
Background
The file box is an indispensable stationery in our daily work, and the existing file box is divided into a paper file box and a plastic file box. Compared with paper file boxes, the plastic file boxes are not easy to mildew and prevent insects, and the development is faster in recent years. However, the plastic file box is made of rubber or plastic, which easily causes environmental pollution, and the plastic file box has slow degradation rate, is easy to form plastic garbage and is not environment-friendly. Compared with a plastic file box, the paper file box can be produced by waste paper, is easy to degrade and is more environment-friendly. However, the wood is easy to grow insects and mildew due to the wood property during the use process, and damages the data in the box.
If a protection against insects mould proof type archives sealed processing apparatus that chinese patent CN110973852A discloses, including archives storage box, anticorrosive case and archives box, archives storage box sets up in anticorrosive case upper end, archives storage box inside is provided with the archives box and places the chamber, anticorrosive incasement portion is provided with the drier, the sealed articulated sealed lid that has on the cavity, archives box rear end upper portion is the arc structure, the lower extreme is the rectangle structure, archives box activity joint is placed on the chamber at the archives box, joint department is provided with buckle subassembly and sealing member. In the invention, the purposes of insect prevention and mildew prevention are achieved through the use of the drying agent, and the drying agent needs to be replaced irregularly, so that the mildew and insect prevention effects of the file box are lost along with the failure of the drying agent.
Therefore, the invention provides the environment-friendly paper file box with the mildew-proof and insect-proof functions, and aims to solve the problems that the existing paper file box is easy to mildew and grow insects.
Disclosure of Invention
The invention aims to provide an environment-friendly paper file box with mildew-proof and insect-proof functions.
The purpose of the invention can be realized by the following technical scheme:
environment-friendly paper file box with mould proof protection against insects function, including the box body, the both sides face of box body all is equipped with the ventilation hole to promote the circulation of air in the box body, avoid mildening and rot of paper data.
Further, the box body is made of mildew-proof and insect-proof paperboard.
Further, the mildew-proof insect-proof paperboard comprises the following components in parts by weight: 95-115 parts of paper pulp, 0.5-1.5 parts of cationic polyacrylamide, 0.3-1 part of silica sol, 15-25 parts of hyperbranched quaternary phosphonium salt and 1.5-3.5 parts of compound essential oil.
Further, the paper pulp comprises the following components in percentage by weight: 15-23% of straw pulp, 40-65% of wood chip pulp and the balance of waste paperboard pulp.
Further, the pulp beating degree is 30-40 DEG SR.
Further, the compound essential oil is formed by mixing lavender essential oil, citronella essential oil and mint essential oil according to the mass ratio of 1-3:0.2-1: 0.6-1.7.
Further, the hyperbranched quaternary phosphonium salt is prepared by the steps of:
s1, adding acetonitrile, a dichloro monomer, trihydroxymethyl phosphine oxide and sodium hydroxide into a four-neck flask which is filled with nitrogen and is provided with a condensation reflux device and a mechanical stirrer, uniformly stirring, heating and refluxing for 14h under the protection of nitrogen, removing a solvent by rotary evaporation, washing for 2-4 times by deionized water and ethanol, and drying in vacuum to constant weight to obtain a hyperbranched nitrogen-phosphorus compound, wherein the molar ratio of the dichloro monomer to the trihydroxymethyl phosphine oxide is 2n +1: n, n is the amount of the substance of the trihydroxymethyl phosphine oxide, and the amount of the substance added with the sodium hydroxide is equal to the amount of the substance of the trihydroxymethyl phosphine oxide;
the reaction utilizes the reaction of chlorine in the dichloro monomer and hydroxyl in the trihydroxymethyl phosphine oxide to generate the hyperbranched nitrogen-phosphorus compound, and the molar ratio of the dichloro monomer to the trihydroxymethyl phosphine oxide is controlled to be 2n +1: n, so that the obtained hyperbranched nitrogen-phosphorus compound is terminated by chlorine, and a foundation is laid for the subsequent reaction;
the molecular structural formula of the hyperbranched nitrogen-phosphorus compound is as follows:
Figure GDA0003641235130000031
wherein, the first and the second end of the pipe are connected with each other,
Figure GDA0003641235130000035
is composed of
Figure GDA0003641235130000032
Figure GDA0003641235130000033
Is composed of
Figure GDA0003641235130000034
S2, adding acetonitrile, a hyperbranched nitrogen-phosphorus compound, 4-hydroxyphenyl bromide and sodium hydroxide into a four-neck flask filled with a condensation reflux device and a mechanical stirrer, uniformly stirring, heating and refluxing for 8h under the protection of nitrogen, removing a solvent by rotary evaporation, washing with deionized water and ethanol for 2-4 times, and drying in vacuum to constant weight to obtain the hyperbranched quaternary phosphonium salt, wherein the molar ratio of the hyperbranched nitrogen-phosphorus compound to the (4-hydroxyphenyl) bromide is 1: m, m is the amount of nitrogen in the hyperbranched nitrogen-phosphorus compound, and the amount of the substance added with the sodium hydroxide is equal to the amount of the (4-hydroxyphenyl) -phenylphosphonium bromide.
In the reaction, chlorine in the hyperbranched nitrogen-phosphorus compound reacts with hydroxyl in the (4-hydroxyphenyl) -phenylphosphonium bromide to obtain hyperbranched quaternary phosphonium salt, and the hyperbranched nitrogen-phosphorus compound is subjected to quaternary phosphonium salinization, so that on one hand, the dissolving capacity of the hyperbranched quaternary phosphonium salt in paper pulp is higher than that of the hyperbranched nitrogen-phosphorus compound, and on the other hand, the antibacterial performance of the hyperbranched quaternary phosphonium salt is improved by accessing the quaternary phosphonium salt; and finally, since the dichloro monomer contains alkyl branched chains, when the hyperbranched quaternary phosphonium salt is dissolved in the paper pulp, the branched chains spontaneously approach and gather to form hydrophobic cavities, and the hydrophobic cavities can contain the compound essential oil to promote the dissolution of the compound essential oil in the paper pulp.
Further, the dichloro monomer is prepared by the following steps:
s11, stirring and reacting hexylamine, methyl acrylate and methanol uniformly, stirring and reacting for 6h at 20-30 ℃, then performing rotary evaporation to remove the methanol, dissolving the obtained product in dichloromethane, stirring fully, dropwise adding 1M HCI solution until the pH is less than 1, then adding deionized water to wash, extracting for 3 times by using dichloromethane, and then performing rotary evaporation to remove the solvent to obtain a dihydroxy intermediate, wherein the molar ratio of hexylamine to methyl acrylate is 1: 2.1-2.3;
s12, adding the dihydroxy intermediate and anhydrous dichloromethane into a three-neck flask with a tail gas treatment device, uniformly stirring, dropwise adding thionyl chloride at a speed of 1-2 drops/second, treating the tail gas with a sodium hydroxide solution, stirring in an ice water bath for reaction for 5 hours, then carrying out suction filtration, washing with dichloromethane for 2-3 times, and carrying out vacuum drying to constant weight to obtain a dichloro monomer, wherein the molar ratio of the dihydroxy intermediate to the thionyl chloride is 1: 3.5-4.5.
The molecular structural formula of the dichloro monomer is shown as follows:
Figure GDA0003641235130000041
further, the (4-hydroxyphenyl) -phenylphosphonium bromide is prepared by the following steps:
adding triphenylphosphine, p-bromophenol, ethylene glycol and nickel bromide into a three-neck flask with a nitrogen introducing device, a stirring device and a thermometer, stirring and reacting for 8h at 180 ℃ under the protection of nitrogen, cooling to room temperature, then dissolving the reactant into dichloromethane, washing for 3-5 times by using deionized water, removing the solvent dichloromethane by rotary evaporation, and drying in vacuum to constant weight to obtain the product of (4-hydroxyphenyl) -phenylphosphonium bromide, wherein the molar ratio of triphenylphosphine to p-bromophenol is 1:1.5-2, and the adding mass of nickel bromide is 3-5% of the mass of triphenylphosphine.
Further, the mildew-proof insect-proof paperboard is prepared by the following method:
defibering paper pulp by using a standard fiber dissociator for 20000 revolutions, adding cationic polyacrylamide and silica sol, uniformly stirring, adding hyperbranched quaternary phosphonium salt and compound essential oil, uniformly stirring, and preparing the mixture into the quantitative 250-containing organic silicon 400g/m by using a sheet-making device2Then using a presser at 2.5kg/cm2Pressurizing for 4-6min, and drying with a drum dryer to obtain the mildew-proof and insect-proof paperboard.
The invention has the beneficial effects that:
according to the invention, the file box is made of the mildew-proof and insect-proof paperboard, the mildew-proof and insect-proof effects of the file box are achieved, a drying agent is not required to be added into the file box, the mildew-proof and insect-proof effects are durable, and the ventilation holes are arranged on the two side surfaces of the file box, so that the circulation of air in the file box can be kept, and the dryness of paper data in the file box is ensured;
the mould-proof and insect-proof paperboard is prepared by adding hyperbranched quaternary phosphonium salt and compound essential oil into paper pulp, and utilizes the antibacterial property of the hyperbranched quaternary phosphonium salt and the insect repelling effect of the compound essential oil; the hyperbranched quaternary phosphonium salt has good water solubility and can be dissolved in paper pulp, the molecular structure of the hyperbranched quaternary phosphonium salt contains a large number of hydrophobic cavities formed by alkyl chains, and the hydrophobic cavities can contain compound essential oil, promote the solubility of the compound essential oil in the paper pulp, solve the compatibility problem of the compound essential oil and the paper pulp, and avoid the phenomenon that the compound essential oil floats on the surface of the paper pulp and finally cannot enter a paperboard in the processing process; the hyperbranched quaternary phosphonium salt contains a large amount of nitrogen and phosphorus elements, so the introduction of the hyperbranched quaternary phosphonium salt increases the flame retardant property of the paperboard, namely the flame retardant property of the file box is increased;
the paper pulp consists of straw pulp, sawdust pulp and waste paperboard pulp, and is environment-friendly;
in conclusion, the paper file box provided by the invention has excellent mildew and insect prevention effects, flame retardant property, environmental protection and economy.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the description below are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
Fig. 1 is a schematic structural view of the environment-friendly paper file box with mildew-proof and insect-proof functions.
In the drawings, the components represented by the respective reference numerals are listed below:
1. a box body; 2. a vent hole.
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.
Referring to fig. 1, the present invention is an environment-friendly paper file box with mildew-proof and insect-proof functions, which includes a box body 1, and two side surfaces of the box body 1 are respectively provided with a vent hole 2.
Example 1:
(4-hydroxyphenyl) -phenylphosphonium bromide was prepared by the following procedure:
0.1mol of triphenylphosphine, 0.15mol of p-bromophenol, 100mL of ethylene glycol and 0.8g of nickel bromide are added into a three-necked bottle with a nitrogen introducing device, a stirring device and a thermometer, the mixture is stirred and reacted for 8h at 180 ℃ under the protection of nitrogen, the mixture is cooled to room temperature, then the reactant is dissolved into dichloromethane, the dichloromethane is washed for 3 times by deionized water, and after the dichloromethane solvent is removed by rotary evaporation, the mixture is dried for 12h in vacuum at 50 ℃ to obtain the product of (4-hydroxyphenyl) -phenylphosphonium bromide.
Example 2:
(4-hydroxyphenyl) -phenylphosphonium bromide was prepared by the following procedure:
0.1mol of triphenylphosphine, 0.2mol of p-bromophenol, 150mL of ethylene glycol and 1.13g of nickel bromide are added into a three-necked bottle with a nitrogen introducing device, a stirring device and a thermometer, the mixture is stirred and reacted for 8h at 180 ℃ under the protection of nitrogen, the mixture is cooled to room temperature, then the reactant is dissolved into dichloromethane, the dichloromethane is washed for 5 times by deionized water, and after the dichloromethane solvent is removed by rotary evaporation, the mixture is dried for 12h in vacuum at 50 ℃ to obtain the product of (4-hydroxyphenyl) -phenylphosphonium bromide.
Example 3:
the dichloro monomer is prepared by the following steps:
s11, stirring 0.1mol of hexylamine, 0.21mol of methyl acrylate and 100mL of methanol uniformly, reacting for 6 hours at 20 ℃, then removing the methanol by rotary evaporation, dissolving the obtained product in 80mL of dichloromethane, stirring fully, dropwise adding 1M HCI solution until the pH is less than 1, then adding 80mL of deionized water for washing, extracting for 3 times by 120mL of dichloromethane, and then removing the solvent by rotary evaporation to obtain a dihydroxy intermediate;
s12, adding 0.1mol of dihydroxy intermediate and 100mL of anhydrous dichloromethane into a three-neck flask with a tail gas treatment device, uniformly stirring, dropwise adding 0.35mol of thionyl chloride at a speed of 1 drop/second, treating the tail gas with 150mL of 1M sodium hydroxide solution, stirring in an ice water bath for 5 hours, carrying out suction filtration, washing for 2 times with dichloromethane, and carrying out vacuum drying at 70 ℃ to constant weight to obtain the dichloro monomer.
Example 4:
the dichloro monomer is prepared by the following steps:
s11, stirring 0.1mol of hexylamine, 0.23mol of methyl acrylate and 150mL of methanol uniformly, then stirring and reacting for 6h at 30 ℃, then performing rotary evaporation to remove the methanol, dissolving the obtained product in 100mL of dichloromethane, fully stirring, dropwise adding a 1M HCI solution until the pH value is less than 1, then adding 100mL of deionized water for washing, extracting for 3 times by using 150mL of dichloromethane, and then performing rotary evaporation to remove the solvent to obtain a dihydroxy intermediate;
s12, adding 0.1mol of dihydroxy intermediate and 100mL of anhydrous dichloromethane into a three-neck flask with a tail gas treatment device, uniformly stirring, dropwise adding 0.45mol of thionyl chloride at a speed of 2 drops/second, treating the tail gas with 150mL of 1M sodium hydroxide solution, stirring in an ice water bath for 5 hours, carrying out suction filtration, washing for 3 times with dichloromethane, and carrying out vacuum drying at 70 ℃ to constant weight to obtain the dichloro monomer.
Example 5:
the hyperbranched quaternary phosphonium salt is prepared by the following steps:
s1, adding 100mL of acetonitrile, 0.3mol of a dichloro monomer prepared in embodiment 3, 0.1mol of tris (hydroxymethyl) phosphine oxide prepared in embodiment 1 and 0.1mol of sodium hydroxide into a four-neck flask which is filled with nitrogen and is provided with a condensation reflux device and a mechanical stirrer, uniformly stirring, heating and refluxing for 14h under the protection of nitrogen, removing a solvent by rotary evaporation, washing for 4 times by using 100mL of deionized water and ethanol (the volume ratio of the deionized water to the ethanol is 1:1), and drying for 24h in a vacuum drying oven at 80 ℃ to obtain the hyperbranched nitrogen-phosphorus compound;
s2, adding 100mL of acetonitrile, 0.01mol of hyperbranched nitrogen-phosphorus compound, 0.03mol of (4-hydroxyphenyl) -phenylphosphonium bromide and 0.03mol of sodium hydroxide into a four-neck flask which is filled with nitrogen and is provided with a condensation reflux device and a mechanical stirrer, uniformly stirring, heating and refluxing for 8h under the protection of nitrogen, removing the solvent by rotary evaporation, washing for 4 times by using 100mL of deionized water and ethanol (the volume ratio of the deionized water to the ethanol is 1:1), and drying in vacuum for 24h at 80 ℃ to obtain the hyperbranched quaternary phosphonium salt.
Example 6:
the hyperbranched quaternary phosphonium salt is prepared by the following steps:
s1, adding 250mL of acetonitrile, 0.7mol of the dichloro monomer prepared in the example 4, 0.3mol of the trimethylol phosphine oxide prepared in the example 2 and 0.3mol of sodium hydroxide into a four-neck flask which is filled with nitrogen and is provided with a condensation reflux device and a mechanical stirrer, uniformly stirring, heating and refluxing for 14h under the protection of nitrogen, removing a solvent by rotary evaporation, washing for 2 times by using 200mL of deionized water and an ethanol solution (the volume ratio of the deionized water to the ethanol is 1:1), and drying in vacuum at 80 ℃ for 24h to obtain the hyperbranched nitrogen-phosphorus compound;
s2, adding 250mL of acetonitrile, 0.01mol of hyperbranched nitrogen-phosphorus compound, 0.07mol of (4-hydroxyphenyl) -phenylphosphonium bromide and 0.07mol of sodium hydroxide into a four-neck flask which is filled with nitrogen and is provided with a condensation reflux device and a mechanical stirrer, uniformly stirring, heating and refluxing for 8h under the protection of nitrogen, removing the solvent by rotary evaporation, washing for 2 times by 200mL of deionized water and ethanol solution (the volume ratio of the deionized water to the ethanol is 1:1), and drying in vacuum at 80 ℃ for 24h to obtain the hyperbranched quaternary phosphonium salt.
Example 7:
the mildew-proof and insect-proof paperboard is prepared by the following method:
taking materials according to the following formula: 95g of paper pulp, 0.5g of cationic polyacrylamide, 0.3g of silica sol, 15g of hyperbranched quaternary phosphonium salt prepared in example 5 and 1.5g of compound essential oil; cationic polyacrylamide was purchased from Narco (Shanghai) trade company, silica sol was purchased from Suzhou Tianma Fine Chemicals, Inc.;
the pulp comprises the following components: 15% of straw pulp, 65% of sawdust pulp and the balance of waste paperboard pulp; the pulp beating degree is 30 DEG SR; the compound essential oil is formed by mixing lavender essential oil, citronella essential oil and mint essential oil according to the mass ratio of 1:0.2: 0.6;
step two, defibering paper pulp by using a standard fiber dissociator for 20000 revolutions, adding cationic polyacrylamide and silica sol, uniformly stirring, adding hyperbranched quaternary phosphonium salt and compound essential oil, uniformly stirring, and making into paper with a sheet making machine to a quantitative of 250g/m2Then using a presser at 2.5kg/cm2Pressurizing for 4min, and drying by a drum dryer to obtain the mildew-proof and insect-proof paperboard.
Example 8:
the mildew-proof and insect-proof paperboard is prepared by the following method:
taking materials according to the following formula: 100g of paper pulp, 1g of cationic polyacrylamide, 0.7g of silica sol, 20g of hyperbranched quaternary phosphonium salt prepared in example 5 and 2g of compound essential oil; cationic polyacrylamide was purchased from Narco (Shanghai) trade company, silica sol was purchased from Suzhou Tianma Fine Chemicals, Inc.;
the pulp comprises the following components: 23% of straw pulp, 40% of wood chip pulp and the balance of waste paperboard pulp; the pulp beating degree is 40 DEG SR; the compound essential oil is formed by mixing lavender essential oil, citronella essential oil and mint essential oil according to the mass ratio of 2:0.5: 1;
step two, defibering paper pulp by using a standard fiber dissociator for 20000 revolutions, adding cationic polyacrylamide and silica sol, stirring uniformly, adding hyperbranched quaternary phosphonium salt and compound essential oil, stirring uniformly, and making into the paper pulp with a sheet making machine to obtain the paper pulp with the quantitative of 400g/m2Then using a presser at 2.5kg/cm2Pressurizing for 6min, and drying by a drum dryer to obtain the mildew-proof and insect-proof paperboard.
Example 9:
the mildew-proof and insect-proof paperboard is prepared by the following method:
taking materials according to the following formula: 115g of paper pulp, 1.5g of cationic polyacrylamide, 1g of silica sol, 25g of hyperbranched quaternary phosphonium salt prepared in example 5 and 3.5g of compound essential oil; cationic polyacrylamide was purchased from Nalcico (Shanghai) trade company, silica sol was purchased from Suzhou Tianma Fine Chemicals, Inc.;
the pulp comprises the following components: 17% of straw pulp, 55% of sawdust pulp and the balance of waste paperboard pulp; the pulp beating degree is 37 DEG SR; the compound essential oil is formed by mixing lavender essential oil, citronella essential oil and mint essential oil according to the mass ratio of 3:1: 1.7;
step two, defibering paper pulp by using a standard fiber dissociator for 20000 revolutions, adding cationic polyacrylamide and silica sol, uniformly stirring, adding hyperbranched quaternary phosphonium salt and compound essential oil, uniformly stirring, and making the paper pulp into paper pulp with the quantitative of 350g/m by using a sheet making machine2Then using a press at 2.5kg/cm2Pressurizing for 5min, and drying by a drum dryer to obtain the mildew-proof and insect-proof paperboard.
Example 10:
environment-friendly paper archives box with mould proof protection against insects function: the mould-proof and insect-proof paperboard prepared in the embodiment 7 is pressed into folding lines according to a plane template of the file box, and is pressed into the vent holes 2, and then the box body 1 is folded according to the folding lines, so that the environment-friendly paper file box with the mould-proof and insect-proof functions is obtained.
Example 11:
environment-friendly paper archives box with mould proof protection against insects function: the mould-proof and insect-proof paperboard prepared in the embodiment 8 is pressed into folding lines according to a plane template of the file box, and is pressed into the vent holes 2, and then the box body 1 is folded and packaged according to the folding lines, so that the environment-friendly paper file box with the mould-proof and insect-proof functions is obtained.
Example 12:
environment-friendly paper archives box with mould proof protection against insects function: the mould-proof and insect-proof paper board prepared in the embodiment 9 is pressed into folding lines according to a plane template of the file box, and is punched to obtain the vent holes 2, and then the box body 1 is folded and assembled according to the folding lines, so that the environment-friendly paper file box with the mould-proof and insect-proof functions is obtained.
Comparative example 1:
the paperboard is made by the following method:
taking materials according to the following formula: 95g of paper pulp, 0.5g of cationic polyacrylamide, 0.3g of silica sol, XT-41115 g of quaternary phosphonium salt and 1.5g of compound essential oil; cationic polyacrylamide was purchased from Narco (Shanghai) trade company, silica sol was purchased from Suzhou Tianma Fine Chemicals, Inc., and quaternary phosphonium salt XT-411 was purchased from Shandong Xintai Water treatment technology, Inc.;
the pulp comprises the following components: 15% of straw pulp, 65% of sawdust pulp and the balance of waste paperboard pulp; the pulp beating degree is 30 DEG SR; the compound essential oil is formed by mixing lavender essential oil, citronella essential oil and mint essential oil according to the mass ratio of 1:0.2: 0.6;
step two, the same as in example 7.
Comparative example 2:
the paperboard is made by the following method:
taking materials according to the following formula: 100g of paper pulp, 1g of cationic polyacrylamide, 0.7g of silica sol and 20g of hyperbranched quaternary phosphonium salt prepared in example 5; cationic polyacrylamide was purchased from Narco (Shanghai) trade company, silica sol was purchased from Suzhou Tianma Fine Chemicals, Inc.;
the pulp comprises the following components: 23% of straw pulp, 40% of wood chip pulp and the balance of waste paperboard pulp; the pulp beating degree is 40 DEG SR; the compound essential oil is formed by mixing lavender essential oil, citronella essential oil and mint essential oil according to the mass ratio of 2:0.5: 1;
step two, the same as step two in example 8.
Comparative example 3:
the paperboard is made by the following method:
taking materials according to the following formula: 115g of paper pulp, 1.5g of cationic polyacrylamide, 1g of silica sol and 3.5g of compound essential oil; cationic polyacrylamide was purchased from Narco (Shanghai) trade company, silica sol was purchased from Suzhou Tianma Fine Chemicals, Inc.;
the pulp comprises the following components: 17% of straw pulp, 55% of sawdust pulp and the balance of waste paperboard pulp; the pulp beating degree is 37 DEG SR; the compound essential oil is formed by mixing lavender essential oil, citronella essential oil and mint essential oil according to the mass ratio of 3:1: 1.7;
step two, the same as step two in example 9.
Comparative example 4:
environment-friendly paper archives box with mould proof protection against insects function: the paperboard prepared in comparative example 1 was used, in contrast to example 10.
Comparative example 5:
environment-friendly paper archives box with mould proof protection against insects function: the paperboard prepared in comparative example 2 was used, in contrast to example 11.
Comparative example 6:
environment-friendly paper archives box with mould proof protection against insects function: the paperboard prepared in comparative example 3 was used in comparison with example 12.
Example 13:
first, 20 of the archival boxes obtained in examples 10-12 and comparative examples 4-6 were taken for containing paper made of the same material, and the archival boxes were divided into two groups, wherein each of the archival boxes obtained in examples 10-12 and comparative examples 4-6 in each group was 10:
the archive boxes obtained in examples 10 to 12 and comparative examples 4 to 6 were placed in closets (material boxes) of different rooms, the environments of the two rooms were kept the same, and the humidity was 45%, and after 3 months of storage, the cases of mildew and vermin were observed, and the results showed that the paper in the archive box obtained in example 10 to 12 did not mildew, the paper in the closet did not vermin, the paper mold rate in the archive box obtained in comparative example 4 was 9.2%, a large number of vermin were present in the closet, the paper in the archive box obtained in comparative example 5 did not mildew, a large number of vermin were present in the closet, the paper mold rate in the archive box obtained in comparative example 6 was 43.4%, and a large number of vermin were present in the closet; from the above, it can be seen that the mildewproof and mothproof functions of the filing cases obtained in examples 10 to 12 are superior to the corresponding performances of the filing cases obtained in comparative examples 3 to 5.
II, limiting oxygen index combustion test: the archive boxes obtained in examples 10 to 12 and comparative examples 4 to 6 were measured according to the GB/T2406.2-2009 standard, which specifies that the test can maintain the minimum oxygen concentration required for the combustion of the sample in a mixed gas flow of oxygen and nitrogen, and is defined as a limiting oxygen index, and the specific operating method was carried out according to the standard, and the test data are shown below.
Figure GDA0003641235130000131
From the above data it can be seen that the flame retardant properties of the archival boxes obtained by examples 10-12 are superior to the corresponding properties of the archival boxes obtained by comparative examples 4, 6.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is merely exemplary and illustrative of the principles of the present invention and various modifications, additions and substitutions of the specific embodiments described herein may be made by those skilled in the art without departing from the principles of the present invention or exceeding the scope of the claims set forth herein.

Claims (7)

1. Environment-friendly paper archives box with mould proof protection against insects function, including box body (1), its characterized in that: both side surfaces of the box body (1) are provided with vent holes (2); the box body (1) is made of mildew-proof and insect-proof paperboard; the mildew-proof insect-proof paperboard comprises the following components: paper pulp, cationic polyacrylamide, silica sol, hyperbranched quaternary phosphonium salt and compound essential oil;
the hyperbranched quaternary phosphonium salt is prepared by the following method:
uniformly stirring acetonitrile, a hyperbranched nitrogen-phosphorus compound, (4-hydroxyphenyl) -phenylphosphonium bromide and sodium hydroxide, heating and refluxing for 8 hours under the protection of nitrogen, carrying out rotary evaporation, washing and vacuum drying to obtain a hyperbranched quaternary phosphonium salt;
the hyperbranched nitrogen-phosphorus compound is prepared by the following steps:
uniformly stirring acetonitrile, a dichloro monomer, trihydroxymethyl phosphine oxide and sodium hydroxide, heating and refluxing for reaction for 14 hours under the protection of nitrogen, and performing rotary evaporation, washing and vacuum drying to obtain a hyperbranched nitrogen-phosphorus compound;
the dichloro monomer is prepared by the following steps:
s11, stirring hexylamine, methyl acrylate and methanol uniformly, reacting for 6 hours at 20-30 ℃, and post-treating to obtain a dihydroxy intermediate;
and S12, uniformly stirring the dihydroxy intermediate and anhydrous dichloromethane, dripping thionyl chloride, stirring in an ice-water bath for reaction for 5 hours, and then carrying out suction filtration, washing and vacuum drying to obtain the dichloro monomer.
2. The environment-friendly paper file box with mildew and insect prevention function as claimed in claim 1, characterized in that: the mole ratio of the hyperbranched nitrogen-phosphorus compound to the (4-hydroxyphenyl) -phenylphosphonium bromide is 1: m, m is the amount of nitrogen in the hyperbranched nitrogen-phosphorus compound, and the amount of the substance added with the sodium hydroxide is equal to the amount of the (4-hydroxyphenyl) -phenylphosphonium bromide.
3. The environment-friendly paper file box with mildew and insect prevention function as claimed in claim 1, characterized in that: the mildew-proof insect-proof paperboard comprises the following components in parts by weight: 95-115 parts of paper pulp, 0.5-1.5 parts of cationic polyacrylamide, 0.3-1 part of silica sol, 15-25 parts of hyperbranched quaternary phosphonium salt and 1.5-3.5 parts of compound essential oil.
4. The environment-friendly paper file box with mildew and insect prevention function as claimed in claim 1, characterized in that: the paper pulp comprises the following components in percentage by weight: 15-23% of straw pulp, 40-65% of wood chip pulp and the balance of waste paperboard pulp.
5. The environment-friendly paper file box with mildew-proof and insect-proof functions as claimed in claim 1, which is characterized in that: the molar ratio of the dichloro monomer to the trihydroxymethyl phosphine oxide is 2n +1: n, n is the amount of the substance of the trihydroxymethyl phosphine oxide, and the amount of the substance added with the sodium hydroxide is equal to the amount of the substance of the trihydroxymethyl phosphine oxide.
6. The environment-friendly paper file box with mildew and insect prevention function as claimed in claim 1, characterized in that: in the step S11, the molar ratio of the hexylamine to the methyl acrylate is 1: 2.1-2.3.
7. The environment-friendly paper file box with mildew and insect prevention function as claimed in claim 1, characterized in that: the molar ratio of the dihydroxy intermediate to the thionyl chloride in step S12 is 1: 3.5-4.5.
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