CN111794012B - High-strength water-resistant flame-retardant plain colored paper and preparation method thereof - Google Patents
High-strength water-resistant flame-retardant plain colored paper and preparation method thereof Download PDFInfo
- Publication number
- CN111794012B CN111794012B CN202010587187.5A CN202010587187A CN111794012B CN 111794012 B CN111794012 B CN 111794012B CN 202010587187 A CN202010587187 A CN 202010587187A CN 111794012 B CN111794012 B CN 111794012B
- Authority
- CN
- China
- Prior art keywords
- styrene
- water
- retardant
- acrylic latex
- montmorillonite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21F—PAPER-MAKING MACHINES; METHODS OF PRODUCING PAPER THEREON
- D21F11/00—Processes for making continuous lengths of paper, or of cardboard, or of wet web for fibre board production, on paper-making machines
-
- 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
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
-
- 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
- D21H17/63—Inorganic compounds
- D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
- D21H17/68—Water-insoluble compounds, e.g. fillers, pigments siliceous, e.g. clays
-
- 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
- D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
- D21H19/20—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
Abstract
The invention discloses high-strength water-resistant flame retardant plain colored paper and a preparation method thereof, and relates to the technical field of flame retardant paper. The high-strength water-resistant flame-retardant plain paper is prepared by using styrene, butyl acrylate and the like as main reaction monomers, lauryl methacrylate and dicyclopentenyl ethoxylated acrylate as functional monomers, sodium dodecyl sulfate and nonylphenol polyoxyethylene ether as emulsifiers, persulfate as an initiator, sodium bicarbonate as a buffering agent and organic modified montmorillonite as a modifier, and synthesizing montmorillonite modified functionalized styrene-acrylic latex by adopting a pre-emulsification seed emulsion polymerization process; then compounding the flame retardant with a flame retardant containing various flame retardant elements to obtain flame retardant styrene-acrylic latex, coating the flame retardant styrene-acrylic latex on the surface of plain paper base paper by using a surface coating method, and drying. The plain color paper prepared by the method has the advantages of excellent dry and wet tensile strength and water resistance, good flame retardance, advanced preparation process, no pollution, lower production cost and wide market application prospect.
Description
Technical Field
The invention relates to the technical field of flame-retardant paper, in particular to high-strength water-resistant flame-retardant plain colored paper and a preparation method thereof.
Background
The scarcity of the global forest resources has prompted the mass production of the veneer, and the plain paper used as the surface decorative material of the veneer has become the widely used decorative material in the furniture industry and the building decoration industry. With the social development and the improvement of the living standard of people, the common plain color paper can not meet the requirements of the veneer material, and if the plain color paper used for indoor decoration needs to be subjected to flame retardant treatment in view of fire safety, the fire hazard of the plain color paper is reduced; from the use effect of furniture, plain color paper also needs to be water-resistant, sun-proof and better in strength to achieve better performance and prolong the service life, so that the plain color paper for high-grade veneer materials needs to be subjected to flame-retardant, water-resistant and enhancement treatment to improve the use characteristics of the plain color paper, and has very important significance for expanding the application range of decorative office furniture, wardrobes, fireproof plates and the like and saving forest resources.
The technical problems to be solved by the invention are as follows:
1. solves the problems of flame retardance, flame retardant efficiency and cost of plain color paper.
The plain color paper is widely applied to decoration of office furniture, wardrobes, fireproof plates and the like, and the main raw material of the plain color paper is inflammable plant fiber, so that the flame retardance is the essential important performance of the plain color paper for indoor decoration, and the flame retardance of the plant fiber is a very important link. The plain color paper is subjected to flame retardant treatment, so that the hidden danger of fire can be reduced, the spreading speed or the spreading tendency of flame can be delayed, and casualties and property loss in the fire can be reduced. However, at present, plain paper is often free of flame retardant treatment, and has great potential safety hazard in use; and the other part of plain color paper realizes flame retardance by adopting a method of adding a flame retardant into pulp, but the general flame retardant has large addition amount, more loss, high cost and large influence on the strength of the paper.
2. Solves the problems of water resistance and strength of plain paper.
The plain color paper needs gum dipping in the subsequent treatment process, so that good dry tensile strength and wet tensile strength are needed; in addition, when the polyurethane resin is used as a surface decorative material, certain water resistance is required, namely, better strength performance and water resistance are required, so that various additives such as a drying strength agent, a wet strength agent and the like are required to be added in the production process, and the polyurethane resin is required to be dipped with melamine glue for treatment, so that the glue solution has large absorption capacity and high production cost, and the problem of large formaldehyde release amount in the use process is solved.
The present application has been made for the above reasons.
Disclosure of Invention
In view of the problems or defects of the prior art, the invention aims to provide high-strength water-resistant flame retardant colored paper and a preparation method thereof.
In order to achieve the first object of the present invention, the present invention adopts the following technical solutions:
a high-strength water-resistant flame-retardant plain paper is prepared by uniformly coating a layer of flame-retardant styrene-acrylic latex on the surface of the base paper of the plain paper, drying, calendering and coiling; wherein: the high-strength water-resistant flame-retardant plain color paper has the quantitative ratio of 50-70 g/m2The limiting oxygen index is 32-36%, the longitudinal dry tensile strength is 25-28N/15 mm, the longitudinal wet tensile strength is 8-10N/15 mm, and the surface water absorption is 30-56 g/m2。
Further, according to the technical scheme, the mass percentage concentration of the flame-retardant styrene-acrylic latex is 0.1-1.0%, and the flame-retardant styrene-acrylic latex is prepared by mixing a composite flame retardant and montmorillonite-modified functional styrene-acrylic latex according to a ratio, and then adding water to mix uniformly.
Furthermore, according to the technical scheme, the mass ratio of the composite flame retardant to the montmorillonite-modified functional styrene-acrylic latex is 1: (1.2-2.0).
Furthermore, according to the technical scheme, the composite flame retardant contains two or more flame retardant elements. For example, the composite flame retardant may be a combination of any two or more of ammonium polyphosphate, melamine polyphosphate, zinc borate, aluminum phosphate, and the like, and the ratio of the flame retardant elements may not be specifically limited.
Preferably, in the technical scheme, the composite flame retardant consists of two or more flame retardant elements with equal mass.
Furthermore, in the technical scheme, the montmorillonite modified functional styrene-acrylic latex is prepared by the following method, and the method comprises the following steps:
(1) preparation of Pre-emulsion
Adding lauryl methacrylate, water, sodium dodecyl sulfate and nonylphenol polyoxyethylene ether into a constant-speed stirrer 1 according to the proportion in sequence, and stirring uniformly; then continuously adding the dicyclopentenyl ethoxylated acrylate, and uniformly stirring; sequentially adding acrylic acid, methyl methacrylate, butyl acrylate and styrene into the reaction system, and stirring at a constant speed until the mixture is uniformly mixed; obtaining pre-emulsion;
(2) preparing montmorillonite modified functional styrene-acrylic latex
(i) Dispersing an initiator in deionized water to obtain an initiator solution;
(ii) sequentially adding water, sodium dodecyl sulfate, nonylphenol polyoxyethylene ether, sodium bicarbonate and organic modified montmorillonite into a reactor 1, and heating a reaction system to 70-90 ℃ under the condition of stirring; slowly adding part of the pre-emulsion obtained in the step (1) and a small amount of the initiator solution obtained in the step (i), and stirring for 0.5-1.5 hours to obtain a seed solution; and continuously and slowly adding the rest pre-emulsion and the initiator solution into the reaction system, continuously carrying out heat preservation reaction for 1-1.5 h at 70-90 ℃ under the stirring condition after the addition is finished, cooling to room temperature after the reaction is finished, filtering, and adjusting the pH value of the product to be neutral to obtain the montmorillonite modified functional styrene-acrylic latex.
Specifically, in the above technical scheme, the structural formula of the dicyclopentenyl ethoxylated acrylate in step (1) is shown as the following formula:
preferably, in the above technical scheme, the dicyclopentenyl ethoxylated acrylate in step (1) is prepared by the following method, which comprises the following steps:
(a) sequentially adding ethylene glycol and dicyclopentadiene into a reactor 2 according to a ratio, continuously and slowly adding p-toluenesulfonic acid, uniformly stirring the obtained reaction solution, gradually heating the temperature of the reaction system to 114-118 ℃, preserving the temperature for 2-3 hours, and cooling to room temperature after the reaction is finished; finally, adding a sodium carbonate aqueous solution, washing with distilled water, and carrying out reduced pressure rectification to obtain ethylene glycol dicyclopentenyl ether;
(b) and (2) sequentially adding a mixture 1 consisting of the ethylene glycol dicyclopentenyl ether prepared in the step (a), acrylic acid, cyclohexane and toluene, a mixture 2 consisting of resorcinol and hydroquinone monomethyl ether and di-n-butyltin oxide into a reactor 3 according to a ratio, uniformly mixing, heating a reaction system to 95-100 ℃, reacting at a constant temperature for 3.5-4.5 hours, cooling to room temperature after the reaction is finished, filtering, and then carrying out normal-pressure distillation separation and reduced-pressure distillation separation to obtain the dicyclopentenyl ethoxylated acrylate.
Preferably, in the above technical solution, the mass ratio of ethylene glycol, dicyclopentadiene, p-toluenesulfonic acid, and sodium carbonate in step (a) is 1: 2: 0.001: 0.0015.
preferably, in the above technical solution, the mass ratio of the ethylene glycol dicyclopentenyl ether, acrylic acid, cyclohexane, toluene, resorcinol, hydroquinone monomethyl ether, and di-n-butyl tin oxide in step (b) is 1: 0.35-0.4: 0.2-0.25: 0.32 to 0.36: 0.0042-0.0048: 0.001-0.0015: 0.0026 to 0.003.
Preferably, in the above technical scheme, the mass ratio of lauryl methacrylate, water, sodium dodecyl sulfate, nonylphenol polyoxyethylene ether, dicyclopentenyl ethoxylated acrylate, acrylic acid, methyl methacrylate, butyl acrylate and styrene in step (1) is 1: 10-20: 0.2-0.4: 0.2-0.4: 1-1.2: 0.3-0.6: 3-5: 30-45: 30-45.
Preferably, in the above technical scheme, the initiator in step (i) is preferably a persulfate, and specifically may be any one of ammonium persulfate, sodium persulfate, and potassium persulfate.
Preferably, in the above technical scheme, the amount ratio of the initiator to the deionized water in the step (i) is (0.5-1) by mass: (10-30) parts by volume; more preferably 0.8 parts by mass: 20 parts by volume; wherein: the mass portion and the volume portion are as follows: mL was used as a reference.
Preferably, in the above technical scheme, the mass ratio of the pre-emulsion in the step (ii), water, sodium dodecyl sulfate, nonylphenol polyoxyethylene ether, sodium bicarbonate, organic modified montmorillonite and initiator is as follows: 1: 0.2-0.3: 0.0025 to 0.003: 0.0025 to 0.003: 0.0025 to 0.003: 0.003-0.008: 0.15 to 0.2.
Further, in the above technical scheme, the pH regulator in step (ii) is preferably an aqueous ammonia solution.
Preferably, in the above technical scheme, the organically modified montmorillonite in step (ii) is prepared by the following method, comprising the following steps:
sequentially adding sodium-based montmorillonite and water into a constant-speed stirrer 2, and stirring to form uniformly dispersed suspension; and then adding octadecyl trimethyl ammonium chloride into the suspension, uniformly mixing, heating the reaction system to 80-85 ℃, reacting for 2-5 h at constant temperature, filtering after the reaction is finished, drying in vacuum, and grinding into powder to obtain the organic modified montmorillonite.
Preferably, in the above technical scheme, the amount of water is not limited as long as the uniform dispersion of the sodium-based montmorillonite can be achieved. For example, the amount ratio of sodium-based montmorillonite to water may be 1 part by mass: (10-50) parts by volume; wherein: the mass portion and the volume portion are as follows: mL was used as a reference.
Preferably, in the technical scheme, the mass ratio of the sodium montmorillonite to the octadecyl trimethyl ammonium chloride is 1: 0.001 to 0.003.
The second purpose of the invention is to provide a preparation method of the high-strength water-resistant flame-retardant plain color paper, which comprises the following steps:
uniformly mixing softwood pulp, hardwood pulp and sulfonated chemi-mechanical pulp according to a ratio to obtain pulp fibers; then adding a composite papermaking auxiliary agent into the pulp fiber, uniformly mixing, and then carrying out flow feeding, wire feeding, squeezing, drying, surface coating, re-drying, soft calendaring and reeling to obtain high-strength water-resistant flame retardant colored paper; wherein: the coating adopted by the surface coating process is flame-retardant styrene-acrylic latex.
Further, according to the technical scheme, the composite papermaking auxiliary agent comprises a wire fiber retention agent and a wire dewatering accelerant.
Preferably, in the technical scheme, the composite papermaking auxiliary agent consists of cationic polyacrylamide and diatomite; wherein: the mass ratio of the slurry fiber to the cationic polyacrylamide to the diatomite is 1: 0.002-0.004: 0.008-0.015.
Further, according to the technical scheme, the softwood pulp and the hardwood pulp are prepared by 2 rows and 2 parallel series-parallel mixed pulp grinding treatment of a disc mill; wherein: the mass percentage concentration of the softwood pulp and the hardwood pulp is 4-5%, and the beating degree is 35-40 DEG SR.
Further, according to the technical scheme, the sulfonated chemi-mechanical pulp is prepared by adopting 1-2 conical pulping machines for fine pulp treatment; wherein: the mass percentage concentration of the sulfonated chemi-mechanical pulp is 4-5%, and the beating degree is 30-35 DEG SR.
Further, according to the technical scheme, the mass ratio of the softwood pulp to the hardwood pulp to the sulfonated chemi-mechanical pulp is 1: 0.5-1: 0.5 to 1.
Further, according to the technical scheme, the mass ratio of the slurry fiber to the flame-retardant styrene-acrylic latex is 1: 0.005-0.01.
The raw materials adopted by the invention have the following functions:
lauryl methacrylate is a long-chain methacrylic acid monomer extracted from renewable resource vegetable oil, has active chemical properties, and can be polymerized with other monomers to perform various addition reactions and esterification reactions. As a soft monomer, the glass transition temperature of the polymer can be lowered, imparting flexibility, durability, and water resistance and cohesive strength to the copolymer film. In the synthesis process of the styrene-acrylic latex, lauryl methacrylate is used as a functional monomer, so that the water resistance and the bonding strength of the styrene-acrylic latex can be improved, and the water resistance and the related physical strength of the plain paper can be improved by permeating paper fibers on the surface.
The dicyclopentenyl ethoxylated acrylate has high reaction activity, can be used as an internal and external cross-linking agent of a polymer, and the obtained polymer has good water resistance and film forming property and is an environment-friendly functional monomer. The dicyclopentenyl ethoxylated acrylate is used as a functional monomer for synthesizing styrene-acrylic latex, so that the film forming property and the water resistance of the styrene-acrylic latex can be improved; the surface of the plain paper is coated in the preparation of the plain paper, so that the plain paper has uniform and good water resistance, and the wet tensile strength and the surface water absorption of the plain paper are favorably adjusted.
When the styrene-acrylic latex modified by the bifunctional monomer is applied to plain color paper, the dry and wet strength of the plain color paper can be effectively improved.
Montmorillonite is a hydrous aluminosilicate nonmetallic mineral with a layered structure, and is widely applied due to good expansibility, ion exchange performance and other properties. The invention adopts the montmorillonite modified styrene-acrylic latex, the lamellar structure of the montmorillonite can be partially peeled off in the latex, so the montmorillonite modified styrene-acrylic latex is uniformly dispersed in the latex, the physical property of the latex can be improved, the gas-liquid barrier property of the latex can also be improved, the water resistance, the heat resistance and the like of the styrene-acrylic latex are improved, and the water resistance and the physical strength property of the prepared plain paper are further improved.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the invention, the flame retardant is added in a way of coating the surface of the composite flame-retardant latex, so that no loss occurs, and the strength of paper is not affected by the addition of the flame retardant.
(2) The invention adopts the high-performance functionalized modified styrene-acrylic latex to replace the traditional additives such as a dry strengthening agent, a wet strengthening agent and the like, so that the plain color paper has good physical strength and water resistance, and can partially replace melamine glue, thereby reducing the absorption amount of the melamine glue solution in the subsequent gum dipping treatment, reducing the release of formaldehyde, improving the use safety and simultaneously reducing the production cost.
(3) The montmorillonite modified functionalized styrene-acrylic latex prepared by the invention is compounded with a flame retardant containing multiple flame-retardant elements to prepare the flame-retardant latex, so that the synergistic flame-retardant effect of the multiple flame-retardant elements can be fully exerted.
(4) The invention has the advantages of advanced preparation process, no pollution, lower production cost, good dry and wet tensile strength, water resistance and flame retardance of the plain color paper and wider market application prospect.
Drawings
FIG. 1 is a flow chart of the preparation process of the high-strength water-resistant flame retardant colored paper of the invention.
Detailed Description
The present invention will be described in further detail below with reference to examples. The present invention is implemented on the premise of the technology of the present invention, and the detailed embodiments and specific procedures are given to illustrate the inventive aspects of the present invention, but the scope of the present invention is not limited to the following embodiments.
Various modifications to the precise description of the invention will be readily apparent to those skilled in the art from the information contained herein without departing from the spirit and scope of the appended claims. It is to be understood that the scope of the invention is not limited to the procedures, properties, or components defined, as these embodiments, as well as others described, are intended to be merely illustrative of particular aspects of the invention. Indeed, various modifications of the embodiments of the invention which are obvious to those skilled in the art or related fields are intended to be covered by the scope of the appended claims.
For a better understanding of the invention, and not as a limitation on the scope thereof, all numbers expressing quantities, percentages, and other numerical values used in this application are to be understood as being modified in all instances by the term "about". Accordingly, unless expressly indicated otherwise, the numerical parameters set forth in the specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained. At the very least, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The preparation method of the high-strength water-resistant flame retardant colored paper comprises the following synthetic routes: styrene, butyl acrylate and the like are used as main reaction monomers, lauryl methacrylate and dicyclopentenyl ethoxylated acrylate are used as functional monomers, lauryl sodium sulfate and nonylphenol polyoxyethylene ether are used as emulsifiers, persulfate is used as an initiator, sodium bicarbonate is used as a buffering agent, and organic modified montmorillonite is used as a modifier, and a pre-emulsification seed emulsion polymerization process is adopted to synthesize montmorillonite modified functionalized styrene-acrylic latex; and then compounding the flame retardant with a flame retardant containing various flame retardant elements to obtain flame retardant styrene-acrylic latex, coating the flame retardant styrene-acrylic latex on the surface of plain paper base paper by using a surface coating method, and drying to obtain the high-strength water-resistant flame retardant plain paper.
Example 1
The high-strength water-resistant flame retardant plain color paper of the embodiment is prepared by the following method:
(1) preparation of Pre-emulsion
(a) Sequentially adding ethylene glycol and dicyclopentadiene into a reactor 2 according to a ratio, continuously and slowly adding p-toluenesulfonic acid, uniformly stirring the obtained reaction solution, gradually heating the temperature of the reaction system to 116 ℃, preserving the temperature for 2.5 hours, and cooling to room temperature after the reaction is finished; finally, adding a sodium carbonate aqueous solution, washing with distilled water, and carrying out reduced pressure rectification to obtain ethylene glycol dicyclopentenyl ether; the mass ratio of the ethylene glycol to the dicyclopentadiene to the p-toluenesulfonic acid to the sodium carbonate is 1: 2: 0.001: 0.0015.
(b) sequentially adding a mixture 1 consisting of the ethylene glycol-based dicyclopentenyl ether prepared in the step (a), acrylic acid, cyclohexane and toluene, a mixture 2 consisting of resorcinol and hydroquinone monomethyl ether and di-n-butyltin oxide into a reactor 3 according to a ratio, uniformly mixing, heating a reaction system to 95-100 ℃, reacting at a constant temperature for 3.5-4.5 hours, cooling to room temperature after the reaction is finished, filtering, and then carrying out normal-pressure distillation separation and reduced-pressure distillation separation to obtain dicyclopentenyl ethoxylated acrylate; wherein: the mass ratio of the ethylene glycol dicyclopentenyl ether to the acrylic acid to the cyclohexane to the toluene to the resorcinol to the hydroquinone monomethyl ether to the di-n-butyl tin oxide is 1: 0.37: 0.22: 0.33: 0.0045: 0.0011: 0.0028.
(c) adding lauryl methacrylate, water, sodium dodecyl sulfate and nonylphenol polyoxyethylene ether into a constant-speed stirrer 1 according to the proportion in sequence, and stirring uniformly; then continuously adding the dicyclopentenyl ethoxylated acrylate prepared in the step (b), and uniformly stirring; sequentially adding acrylic acid, methyl methacrylate, butyl acrylate and styrene into the reaction system, and stirring at a constant speed until the mixture is uniformly mixed; obtaining pre-emulsion; wherein: the mass ratio of lauryl methacrylate, water, sodium dodecyl sulfate, nonylphenol polyoxyethylene ether, dicyclopentenyl ethoxylated acrylate, acrylic acid, methyl methacrylate, butyl acrylate and styrene is 1: 10: 0.2: 0.2: 1: 0.3: 3: 30: 30.
(2) preparing montmorillonite modified functional styrene-acrylic latex
(i) Preparing initiator solution
0.8g of ammonium persulfate was weighed and dissolved in 20mL of deionized water to obtain an initiator solution.
(ii) Preparation of organically modified montmorillonite
Sequentially adding 1g of sodium montmorillonite and 10mL of water into a constant-speed stirrer 2, and stirring to form uniformly dispersed suspension; and then adding 0.001g of octadecyl trimethyl ammonium chloride into the suspension, uniformly mixing, heating the reaction system to 80 ℃, reacting for 5 hours at constant temperature, filtering after the reaction is finished, drying in vacuum at 80 ℃, and grinding into powder to obtain the organic modified montmorillonite.
(iii) Preparing montmorillonite modified functional styrene-acrylic latex
Adding water, sodium dodecyl sulfate, nonylphenol polyoxyethylene ether, sodium bicarbonate and the organic modified montmorillonite prepared in the step (ii) into a reactor in sequence, and heating a reaction system to 80 ℃ under the condition of stirring; slowly adding part of the pre-emulsion obtained in the step (1) and a small amount of the initiator solution obtained in the step (i), and stirring for 1h to obtain a seed solution; continuously and slowly adding the rest pre-emulsion and the initiator solution into the reaction system, continuously carrying out heat preservation reaction for 1h at the temperature of 80 ℃ under the stirring condition after the addition is finished, cooling to room temperature after the reaction is finished, filtering, and adjusting the pH value of the product to be neutral by using an ammonia water solution to obtain montmorillonite modified functional styrene-acrylic latex;
wherein: the mass ratio of the pre-emulsion to water to sodium dodecyl sulfate to polyoxyethylene nonyl phenyl ether to sodium bicarbonate to the organic modified montmorillonite to the initiator is 1: 0.2: 0.0025: 0.0025: 0.0025: 0.003: 0.15. it should be noted that, the mass of the pre-emulsion described herein is the sum of the masses of the pre-emulsions added twice in sequence in step (iii); similarly, the mass of the initiator is also the sum of the masses of the initiators added in the step (iii) in two times.
(3) Preparation of flame-retardant styrene-acrylic latex
Uniformly mixing the composite flame retardant and the montmorillonite-modified functional styrene-acrylic latex obtained in the step (2) according to the ratio, and then adding 1000mL of water to prepare flame-retardant styrene-acrylic latex with the mass percentage concentration of 0.1%;
wherein: the composite flame retardant is prepared from the following components in percentage by mass of 1: 1 of ammonium polyphosphate and polyphosphoester;
the mass ratio of the composite flame retardant to the montmorillonite-modified functional styrene-acrylic latex is 1: 1.2, the total mass is 1 g.
(4) Mixing the components in a mass ratio of 1: 0.5: 0.5 of softwood pulp, hardwood pulp and sulfonated chemi-mechanical pulp are mixed uniformly to obtain pulp fibers; then adding a composite papermaking auxiliary agent consisting of cationic polyacrylamide and diatomite into the pulp fibers, uniformly mixing, and then carrying out flow feeding, net feeding, squeezing, drying, surface coating, re-drying, soft press polishing and reeling to obtain high-strength water-resistant flame retardant colored paper; the coating adopted by the surface coating process is the flame-retardant styrene-acrylic latex prepared in the step (3);
wherein: the softwood pulp and the hardwood pulp are prepared by adopting 2 rows and 2 parallel series-parallel mixed pulping treatments of a disc mill; the mass percentage concentration of the softwood pulp is 4%, and the beating degree is 35-degree SR; the mass percentage concentration of the hardwood pulp is 4%, and the beating degree is 35 DEG SR;
the sulfonated chemi-mechanical pulp is prepared by adopting 1-2 conical pulping machines for fine pulp treatment, wherein the mass percentage concentration of the sulfonated chemi-mechanical pulp is 4%, and the beating degree is 30 DEG SR.
The mass ratio of the slurry fiber to the cationic polyacrylamide to the diatomite is 1: 0.002: 0.008;
the mass ratio of the slurry fiber to the flame-retardant styrene-acrylic latex is 1: 0.005.
example 2
The high-strength water-resistant flame retardant plain color paper of the embodiment is prepared by the following method:
(1) preparation of Pre-emulsion
(a) Sequentially adding ethylene glycol and dicyclopentadiene into a reactor 2 according to a ratio, continuously and slowly adding p-toluenesulfonic acid, uniformly stirring the obtained reaction solution, gradually heating the temperature of the reaction system to 114 ℃, preserving the temperature for 3 hours, and cooling to room temperature after the reaction is finished; finally, adding a sodium carbonate aqueous solution, washing with distilled water, and carrying out reduced pressure rectification to obtain ethylene glycol dicyclopentenyl ether; the mass ratio of the ethylene glycol to the dicyclopentadiene to the p-toluenesulfonic acid to the sodium carbonate is 1: 2: 0.001: 0.0015.
(b) sequentially adding a mixture 1 consisting of the ethylene glycol dicyclopentenyl ether prepared in the step (a), acrylic acid, cyclohexane and toluene, a mixture 2 consisting of resorcinol and hydroquinone monomethyl ether and di-n-butyltin oxide into a reactor 3 according to a ratio, uniformly mixing, heating a reaction system to 95 ℃, reacting at a constant temperature for 4.5 hours, cooling to room temperature after the reaction is finished, filtering, and then carrying out normal-pressure distillation separation and reduced-pressure distillation separation to obtain dicyclopentenyl ethoxylated acrylate; wherein: the mass ratio of the ethylene glycol dicyclopentenyl ether to the acrylic acid to the cyclohexane to the toluene to the resorcinol to the hydroquinone monomethyl ether to the di-n-butyl tin oxide is 1: 0.35: 0.2: 0.32: 0.0042: 0.001: 0.0026.
(c) adding lauryl methacrylate, water, sodium dodecyl sulfate and nonylphenol polyoxyethylene ether into a constant-speed stirrer 1 according to the proportion in sequence, and stirring uniformly; then continuously adding the dicyclopentenyl ethoxylated acrylate prepared in the step (b), and uniformly stirring; sequentially adding acrylic acid, methyl methacrylate, butyl acrylate and styrene into the reaction system, and stirring at a constant speed until the mixture is uniformly mixed; obtaining pre-emulsion; wherein: the mass ratio of lauryl methacrylate, water, sodium dodecyl sulfate, nonylphenol polyoxyethylene ether, dicyclopentenyl ethoxylated acrylate, acrylic acid, methyl methacrylate, butyl acrylate and styrene is 1: 12: 0.25: 0.25: 1: 0.4: 4: 35: 35.
(2) preparing montmorillonite modified functional styrene-acrylic latex
(i) Preparing initiator solution
0.5g of ammonium persulfate was weighed and dissolved in 10mL of deionized water to obtain an initiator solution.
(ii) Preparation of organically modified montmorillonite
Sequentially adding 1g of sodium montmorillonite and 20mL of water into a constant-speed stirrer 2, and stirring to form uniformly dispersed suspension; and then adding 0.0015g of octadecyl trimethyl ammonium chloride into the suspension, uniformly mixing, heating the reaction system to 80 ℃, reacting for 4 hours at constant temperature, filtering after the reaction is finished, drying for 2 hours in vacuum at 80 ℃, and grinding into powder to obtain the organic modified montmorillonite.
(iii) Preparing montmorillonite modified functional styrene-acrylic latex
Adding water, sodium dodecyl sulfate, nonylphenol polyoxyethylene ether, sodium bicarbonate and the organic modified montmorillonite prepared in the step (ii) into a reactor in sequence, and heating a reaction system to 70 ℃ under the stirring condition; slowly adding part of the pre-emulsion obtained in the step (1) and a small amount of the initiator solution obtained in the step (i), and stirring for 1.5 hours to obtain a seed solution; continuously and slowly adding the rest pre-emulsion and the initiator solution into the reaction system, continuously carrying out heat preservation reaction for 1.5h at 70 ℃ under the stirring condition after the addition is finished, cooling to room temperature after the reaction is finished, filtering, and adjusting the pH value of the product to be neutral by using an ammonia water solution to obtain montmorillonite modified functional styrene-acrylic latex;
wherein: the mass ratio of the pre-emulsion to water to sodium dodecyl sulfate to polyoxyethylene nonyl phenyl ether to sodium bicarbonate to the organic modified montmorillonite to the initiator is 1: 0.25: 0.003: 0.0025: 0.003: 0.005: 0.18. it should be noted that, the mass of the pre-emulsion described herein is the sum of the masses of the pre-emulsions added twice in sequence in step (iii); similarly, the mass of the initiator is also the sum of the masses of the initiators added in the step (iii) in two times.
(3) Preparation of flame-retardant styrene-acrylic latex
Uniformly mixing the composite flame retardant and the montmorillonite-modified functional styrene-acrylic latex obtained in the step (2) according to the ratio, and then adding 200mL of water to prepare flame-retardant styrene-acrylic latex with the mass percentage concentration of 0.5%;
wherein: the composite flame retardant is prepared from the following components in percentage by mass of 1: 1: 1, polyphosphate ester, melamine polyphosphate ester and zinc borate;
the mass ratio of the composite flame retardant to the montmorillonite-modified functional styrene-acrylic latex is 1: 1.5, the total mass is 1 g.
(5) Mixing the components in a mass ratio of 1: 0.5: 1, uniformly mixing the softwood pulp, the hardwood pulp and the sulfonated chemi-mechanical pulp to obtain pulp fibers; then adding a composite papermaking auxiliary agent consisting of cationic polyacrylamide and diatomite into the pulp fibers, uniformly mixing, and then carrying out flow feeding, net feeding, squeezing, drying, surface coating, re-drying, soft press polishing and reeling to obtain high-strength water-resistant flame retardant colored paper; the coating adopted by the surface coating process is the flame-retardant styrene-acrylic latex prepared in the step (3);
wherein: the softwood pulp and the hardwood pulp are prepared by adopting 2 rows and 2 parallel series-parallel mixed pulping treatments of a disc mill; the mass percentage concentration of the softwood pulp is 4.5%, and the beating degree is 35 DEG SR; the mass percentage concentration of the hardwood pulp is 4.5%, and the beating degree is 35 DEG SR;
the sulfonated chemi-mechanical pulp is prepared by adopting 1-2 conical pulping machines for fine pulp treatment, wherein the mass percentage concentration of the sulfonated chemi-mechanical pulp is 4.5%, and the beating degree is 35 DEG SR.
The mass ratio of the slurry fiber to the cationic polyacrylamide to the diatomite is 1: 0.003: 0.009;
the mass ratio of the slurry fiber to the flame-retardant styrene-acrylic latex is 1: 0.006.
example 3
The high-strength water-resistant flame retardant plain color paper of the embodiment is prepared by the following method:
(1) preparation of Pre-emulsion
(a) Sequentially adding ethylene glycol and dicyclopentadiene into a reactor 2 according to a ratio, continuously and slowly adding p-toluenesulfonic acid, uniformly stirring the obtained reaction solution, gradually heating the temperature of the reaction system to 118 ℃, preserving the temperature for 2 hours, and cooling to room temperature after the reaction is finished; finally, adding a sodium carbonate aqueous solution, washing with distilled water, and carrying out reduced pressure rectification to obtain ethylene glycol dicyclopentenyl ether; wherein: the mass ratio of the ethylene glycol to the dicyclopentadiene to the p-toluenesulfonic acid to the sodium carbonate is 1: 2: 0.001: 0.0015.
(b) sequentially adding a mixture 1 consisting of the ethylene glycol dicyclopentenyl ether prepared in the step (a), acrylic acid, cyclohexane and toluene, a mixture 2 consisting of resorcinol and hydroquinone monomethyl ether and di-n-butyltin oxide into a reactor 3 according to a ratio, uniformly mixing, heating a reaction system to 100 ℃, reacting at a constant temperature for 3.5 hours, cooling to room temperature after the reaction is finished, filtering, and then carrying out normal-pressure distillation separation and reduced-pressure distillation separation to obtain dicyclopentenyl ethoxylated acrylate; wherein: the mass ratio of the ethylene glycol dicyclopentenyl ether to the acrylic acid to the cyclohexane to the toluene to the resorcinol to the hydroquinone monomethyl ether to the di-n-butyl tin oxide is 1: 0.4: 0.25: 0.36: 0.0048: 0.0015: 0.003.
(c) adding lauryl methacrylate, water, sodium dodecyl sulfate and nonylphenol polyoxyethylene ether into a constant-speed stirrer 1 according to the proportion in sequence, and stirring uniformly; then continuously adding the dicyclopentenyl ethoxylated acrylate prepared in the step (b), and uniformly stirring; sequentially adding acrylic acid, methyl methacrylate, butyl acrylate and styrene into the reaction system, and stirring at a constant speed until the mixture is uniformly mixed; obtaining pre-emulsion;
wherein: the mass ratio of lauryl methacrylate, water, sodium dodecyl sulfate, nonylphenol polyoxyethylene ether, dicyclopentenyl ethoxylated acrylate, acrylic acid, methyl methacrylate, butyl acrylate and styrene is 1: 15: 0.3: 0.3: 1.1: 0.4: 4: 40: 40.
(2) preparing montmorillonite modified functional styrene-acrylic latex
(i) Preparing initiator solution
0.6g of potassium persulfate was weighed out and dissolved in 15mL of deionized water to obtain an initiator solution.
(ii) Preparation of organically modified montmorillonite
Sequentially adding 1g of sodium montmorillonite and 30mL of water into a constant-speed stirrer 2, and stirring to form uniformly dispersed suspension; and then adding 0.002g of octadecyl trimethyl ammonium chloride into the suspension, uniformly mixing, heating the reaction system to 85 ℃, reacting for 2 hours at constant temperature, filtering after the reaction is finished, drying for 2 hours in vacuum at 80 ℃, and grinding into powder to obtain the organic modified montmorillonite.
(iii) Preparing montmorillonite modified functional styrene-acrylic latex
Adding water, sodium dodecyl sulfate, nonylphenol polyoxyethylene ether, sodium bicarbonate and the organic modified montmorillonite prepared in the step (ii) into a reactor in sequence, and heating a reaction system to 90 ℃ under the stirring condition; slowly adding part of the pre-emulsion obtained in the step (1) and a small amount of the initiator solution obtained in the step (i), and stirring for 0.5h to obtain a seed solution; continuously and slowly adding the rest pre-emulsion and the initiator solution into the reaction system, continuously carrying out heat preservation reaction for 1h at 90 ℃ under the stirring condition after the addition is finished, cooling to room temperature after the reaction is finished, filtering, and adjusting the pH value of the product to be neutral by using an ammonia water solution to obtain montmorillonite modified functional styrene-acrylic latex;
wherein: the mass ratio of the pre-emulsion to water to sodium dodecyl sulfate to polyoxyethylene nonyl phenyl ether to sodium bicarbonate to the organic modified montmorillonite to the initiator is 1: 0.3: 0.003: 0.0028: 0.0028: 0.006: 0.2. it should be noted that, the mass of the pre-emulsion described herein is the sum of the masses of the pre-emulsions added twice in sequence in step (iii); similarly, the mass of the initiator is also the sum of the masses of the initiators added in the step (iii) in two times.
(3) Preparation of flame-retardant styrene-acrylic latex
Uniformly mixing the composite flame retardant and the montmorillonite-modified functional styrene-acrylic latex obtained in the step (2) according to the ratio, and then adding 250mL of water to prepare flame-retardant styrene-acrylic latex with the mass percentage concentration of 0.4%;
wherein: the composite flame retardant is prepared from the following components in percentage by mass of 1: 1: 1 of melamine polyphosphate, zinc borate and aluminum phosphate;
the mass ratio of the composite flame retardant to the montmorillonite-modified functional styrene-acrylic latex is 1: 1.6, the total mass is 1 g.
(6) Mixing the components in a mass ratio of 1: 0.8: 0.8 of softwood pulp, hardwood pulp and sulfonated chemi-mechanical pulp are mixed uniformly to obtain pulp fibers; then adding a composite papermaking auxiliary agent consisting of cationic polyacrylamide and diatomite into the pulp fibers, uniformly mixing, and then carrying out flow feeding, net feeding, squeezing, drying, surface coating, re-drying, soft press polishing and reeling to obtain high-strength water-resistant flame retardant colored paper; the coating adopted by the surface coating process is the flame-retardant styrene-acrylic latex prepared in the step (3);
wherein: the softwood pulp and the hardwood pulp are prepared by adopting 2 rows and 2 parallel series-parallel mixed pulping treatments of a disc mill; the mass percentage concentration of the softwood pulp is 4%, and the beating degree is 40-degree SR; the mass percentage concentration of the hardwood pulp is 4%, and the beating degree is 40-degree SR;
the sulfonated chemi-mechanical pulp is prepared by adopting 1-2 conical pulping machines for fine pulp treatment, wherein the mass percentage concentration of the sulfonated chemi-mechanical pulp is 5%, and the beating degree is 30 DEG SR.
The mass ratio of the slurry fiber to the cationic polyacrylamide to the diatomite is 1: 0.0025: 0.01;
the mass ratio of the slurry fiber to the flame-retardant styrene-acrylic latex is 1: 0.008.
example 4
The high-strength water-resistant flame retardant plain color paper of the embodiment is prepared by the following method:
(1) preparation of Pre-emulsion
(a) Sequentially adding ethylene glycol and dicyclopentadiene into a reactor 2 according to the proportion, continuously and slowly adding p-toluenesulfonic acid, uniformly stirring the obtained reaction solution, gradually heating the temperature of the reaction system to 115 ℃, preserving the temperature for 2.5 hours, and cooling to room temperature after the reaction is finished; finally, adding a sodium carbonate aqueous solution, washing with distilled water, and carrying out reduced pressure rectification to obtain ethylene glycol dicyclopentenyl ether; wherein: the mass ratio of the ethylene glycol to the dicyclopentadiene to the p-toluenesulfonic acid to the sodium carbonate is 1: 2: 0.001: 0.0015.
(b) sequentially adding a mixture 1 consisting of the ethylene glycol dicyclopentenyl ether prepared in the step (a), acrylic acid, cyclohexane and toluene, a mixture 2 consisting of resorcinol and hydroquinone monomethyl ether and di-n-butyltin oxide into a reactor 3 according to a ratio, uniformly mixing, heating a reaction system to 98 ℃, reacting at a constant temperature for 4 hours, cooling to room temperature after the reaction is finished, filtering, and then carrying out normal-pressure distillation separation and reduced-pressure distillation separation to obtain dicyclopentenyl ethoxylated acrylate; wherein: the mass ratio of the ethylene glycol dicyclopentenyl ether to the acrylic acid to the cyclohexane to the toluene to the resorcinol to the hydroquinone monomethyl ether to the di-n-butyl tin oxide is 1: 0.36: 0.24: 0.35: 0.0046: 0.0012: 0.0028.
(c) adding lauryl methacrylate, water, sodium dodecyl sulfate and nonylphenol polyoxyethylene ether into a constant-speed stirrer 1 according to the proportion in sequence, and stirring uniformly; then continuously adding the dicyclopentenyl ethoxylated acrylate prepared in the step (b), and uniformly stirring; sequentially adding acrylic acid, methyl methacrylate, butyl acrylate and styrene into the reaction system, and stirring at a constant speed until the mixture is uniformly mixed; obtaining pre-emulsion; wherein: the mass ratio of lauryl methacrylate, water, sodium dodecyl sulfate, nonylphenol polyoxyethylene ether, dicyclopentenyl ethoxylated acrylate, acrylic acid, methyl methacrylate, butyl acrylate and styrene is 1: 20: 0.4: 0.4: 1.2: 0.6: 5: 45: 45.
(2) preparing montmorillonite modified functional styrene-acrylic latex
(i) Preparing initiator solution
1.0g of sodium persulfate was weighed out and dissolved in 30mL of deionized water to obtain an initiator solution.
(ii) Preparation of organically modified montmorillonite
Sequentially adding 1g of sodium montmorillonite and 50mL of water into a constant-speed stirrer 2, and stirring to form uniformly dispersed suspension; and then adding 0.003g of octadecyl trimethyl ammonium chloride into the suspension, uniformly mixing, heating the reaction system to 85 ℃, reacting for 3 hours at constant temperature, filtering after the reaction is finished, drying for 2 hours in vacuum at the temperature of 80 ℃, and grinding into powder to obtain the organic modified montmorillonite.
(iii) Preparing montmorillonite modified functional styrene-acrylic latex
Adding water, sodium dodecyl sulfate, nonylphenol polyoxyethylene ether, sodium bicarbonate and the organic modified montmorillonite prepared in the step (ii) into a reactor in sequence, and heating a reaction system to 85 ℃ under the stirring condition; slowly adding part of the pre-emulsion obtained in the step (1) and a small amount of the initiator solution obtained in the step (i), and stirring for 1h to obtain a seed solution; continuously and slowly adding the rest pre-emulsion and the initiator solution into the reaction system, continuously carrying out heat preservation reaction at 85 ℃ for 1.5h under the stirring condition after the addition is finished, cooling to room temperature after the reaction is finished, filtering, and adjusting the pH value of the product to be neutral by using an ammonia water solution to obtain montmorillonite modified functional styrene-acrylic latex;
wherein: the mass ratio of the pre-emulsion to water to sodium dodecyl sulfate to polyoxyethylene nonyl phenyl ether to sodium bicarbonate to the organic modified montmorillonite to the initiator is 1: 0.3: 0.003: 0.003: 0.003: 0.008: 0.2. it should be noted that, the mass of the pre-emulsion described herein is the sum of the masses of the pre-emulsions added twice in sequence in step (iii); similarly, the mass of the initiator is also the sum of the masses of the initiators added in the step (iii) in two times.
(3) Preparation of flame-retardant styrene-acrylic latex
Uniformly mixing the composite flame retardant and the montmorillonite-modified functional styrene-acrylic latex obtained in the step (2) according to the ratio, and then adding 100mL of water to prepare flame-retardant styrene-acrylic latex with the mass percentage concentration of 1.0%;
wherein: the composite flame retardant is prepared from the following components in percentage by mass of 1: 1: 1: 1, ammonium polyphosphate, zinc borate and aluminum phosphate;
the mass ratio of the composite flame retardant to the montmorillonite-modified functional styrene-acrylic latex is 1: 1.2, the total mass is 1 g.
(4) Mixing the components in a mass ratio of 1: 1: 1, uniformly mixing the softwood pulp, the hardwood pulp and the sulfonated chemi-mechanical pulp to obtain pulp fibers; then adding a composite papermaking auxiliary agent consisting of cationic polyacrylamide and diatomite into the pulp fibers, uniformly mixing, and then carrying out flow feeding, net feeding, squeezing, drying, surface coating, re-drying, soft press polishing and reeling to obtain high-strength water-resistant flame retardant colored paper; the coating adopted by the surface coating process is the flame-retardant styrene-acrylic latex prepared in the step (3);
wherein: the softwood pulp and the hardwood pulp are prepared by adopting 2 rows and 2 parallel series-parallel mixed pulping treatments of a disc mill; the mass percentage concentration of the softwood pulp is 5%, and the beating degree is 35-degree SR; the mass percentage concentration of the hardwood pulp is 4%, and the beating degree is 35 DEG SR;
the sulfonated chemi-mechanical pulp is prepared by adopting 1-2 conical pulping machines for fine pulp treatment, wherein the mass percentage concentration of the sulfonated chemi-mechanical pulp is 5%, and the beating degree is 35 DEG SR.
The mass ratio of the slurry fiber to the cationic polyacrylamide to the diatomite is 1: 0.004: 0.015;
the mass ratio of the slurry fiber to the flame-retardant styrene-acrylic latex is 1: 0.01.
the main performance indexes of the high-strength water-resistant flame retardant colored paper prepared in the examples 1 to 4 were tested. The flame retardance is tested by an oxygen index meter according to ASTM D2863 standard, the physical properties are tested according to the national standard GB T12914-2008 of determination of tensile strength of paper and paperboard, and the test results of the surface water absorption are shown in Table 1 according to GB/T1540-2002 test method of water absorption of paper and paperboard.
TABLE 1 test results of main performance indexes of high-strength water-resistant flame retardant colored paper prepared in examples 1 to 4
| Technical index | Example 1 | Example 2 | Example 3 | Example 4 |
| Quantitative g/m2 | 50 | 65 | 52 | 70 |
| Flame retardancy (% limiting oxygen index) | 32 | 35.2 | 32.5 | 36 |
| Longitudinal dry tensile strength N/15mm | 25 | 26.8 | 26.2 | 28 |
| Longitudinal wet tensile strength N/15mm | 8 | 9.4 | 8.2 | 10 |
| Surface water absorption g/m2 | 30 | 45 | 34 | 56 |
Claims (3)
1. The high-strength water-resistant flame-retardant plain color paper is characterized in that: uniformly coating a layer of flame-retardant styrene-acrylic latex on the surface of plain paper base paper, and then drying, calendering and reeling to obtain the flame-retardant styrene-acrylic latex; wherein: the high-strength water-resistant flame-retardant plain color paper has the quantitative ratio of 50-70 g/m2The limiting oxygen index is 32-36%, the longitudinal dry tensile strength is 25-28N/15 mm, the longitudinal wet tensile strength is 8-10N/15 mm, and the surface water absorption is 30-56 g/m2；
The mass percentage concentration of the flame-retardant styrene-acrylic latex is 0.1-1.0%; the flame-retardant styrene-acrylic latex is prepared by mixing a composite flame retardant and montmorillonite-modified functional styrene-acrylic latex in a mass ratio of 1: 1.2-2.0, and then adding water and mixing uniformly to obtain the product; the composite flame retardant is a combination of any two or more of ammonium polyphosphate, zinc borate and aluminum phosphate;
the montmorillonite modified functional styrene-acrylic latex is prepared by the following method, and the method comprises the following steps:
(1) preparation of Pre-emulsion
Adding lauryl methacrylate, water, sodium dodecyl sulfate and nonylphenol polyoxyethylene ether into a constant-speed stirrer 1 according to the proportion in sequence, and stirring uniformly; then continuously adding the dicyclopentenyl ethoxylated acrylate, and uniformly stirring; sequentially adding acrylic acid, methyl methacrylate, butyl acrylate and styrene into the reaction system, and stirring at a constant speed until the mixture is uniformly mixed; obtaining pre-emulsion; the mass ratio of lauryl methacrylate, water, sodium dodecyl sulfate, nonylphenol polyoxyethylene ether, dicyclopentenyl ethoxylated acrylate, acrylic acid, methyl methacrylate, butyl acrylate and styrene is as follows: 1: 10-20: 0.2-0.4: 0.2-0.4: 1-1.2: 0.3-0.6: 3-5: 30-45: 30-45 parts of;
the dicyclopentenyl ethoxylated acrylate is prepared by the following method, and the steps are as follows:
(a) sequentially adding ethylene glycol and dicyclopentadiene into a reactor 2 according to a ratio, continuously and slowly adding p-toluenesulfonic acid, uniformly stirring the obtained reaction solution, gradually heating the temperature of the reaction system to 114-118 ℃, preserving the temperature for 2-3 hours, and cooling to room temperature after the reaction is finished; finally, adding a sodium carbonate aqueous solution, washing with distilled water, and carrying out reduced pressure rectification to obtain ethylene glycol dicyclopentenyl ether; wherein: the mass ratio of the ethylene glycol to the dicyclopentadiene to the p-toluenesulfonic acid to the sodium carbonate is 1: 2: 0.001: 0.0015;
(b) sequentially adding a mixture 1 consisting of the ethylene glycol-based dicyclopentenyl ether prepared in the step (a), acrylic acid, cyclohexane and toluene, a mixture 2 consisting of resorcinol and hydroquinone monomethyl ether and di-n-butyltin oxide into a reactor 3 according to a ratio, uniformly mixing, heating a reaction system to 95-100 ℃, reacting at a constant temperature for 3.5-4.5 hours, cooling to room temperature after the reaction is finished, filtering, and then carrying out normal-pressure distillation separation and reduced-pressure distillation separation to obtain dicyclopentenyl ethoxylated acrylate; wherein: the mass ratio of the ethylene glycol dicyclopentenyl ether to the acrylic acid to the cyclohexane to the toluene to the resorcinol to the hydroquinone monomethyl ether to the di-n-butyl tin oxide is 1: 0.35-0.4: 0.2-0.25: 0.32 to 0.36: 0.0042-0.0048: 0.001-0.0015: 0.0026 to 0.003;
(2) preparation of montmorillonite modified functionalized styrene-acrylic latex
(i) Dispersing an initiator in deionized water to obtain an initiator solution;
(ii) sequentially adding water, sodium dodecyl sulfate, nonylphenol polyoxyethylene ether, sodium bicarbonate and organic modified montmorillonite into a reactor 1, and heating a reaction system to 70-90 ℃ under the condition of stirring; slowly adding part of the pre-emulsion obtained in the step (1) and a small amount of the initiator solution obtained in the step (i), and stirring for 0.5-1.5 hours to obtain a seed solution; continuously and slowly adding the rest pre-emulsion and the initiator solution into the reaction system, continuously carrying out heat preservation reaction for 1-1.5 h at 70-90 ℃ under the stirring condition after the addition is finished, cooling to room temperature after the reaction is finished, filtering, and adjusting the pH value of the product to be neutral to obtain the montmorillonite modified functional styrene-acrylic latex; the mass ratio of the pre-emulsion to the water to the sodium dodecyl sulfate to the nonylphenol polyoxyethylene ether to the sodium bicarbonate to the organic modified montmorillonite to the initiator is as follows: 1: 0.2-0.3: 0.0025 to 0.003: 0.0025 to 0.003: 0.0025 to 0.003: 0.003-0.008: 0.15 to 0.2;
the organic modified montmorillonite in the step (ii) is prepared by the following method, and the steps are as follows:
sequentially adding sodium-based montmorillonite and water into a constant-speed stirrer 2, and stirring to form uniformly dispersed suspension; adding octadecyl trimethyl ammonium chloride into the suspension, uniformly mixing, heating a reaction system to 80-85 ℃, reacting for 2-5 hours at constant temperature, filtering after the reaction is finished, drying in vacuum, and grinding into powder to obtain the organic modified montmorillonite; the mass ratio of the sodium montmorillonite to the octadecyl trimethyl ammonium chloride is 1: 0.001 to 0.003.
2. The method for preparing the high-strength water-resistant flame retardant pigmented paper according to claim 1, characterized in that: the method comprises the following steps:
according to the mass ratio of 1: 0.5-1: uniformly mixing softwood pulp, hardwood pulp and sulfonated chemi-mechanical pulp in a ratio of 0.5-1 to obtain pulp fibers; then adding a composite papermaking auxiliary agent into the pulp fiber, uniformly mixing, and then carrying out flow feeding, wire feeding, squeezing, drying, surface coating, re-drying, soft calendaring and reeling to obtain high-strength water-resistant flame retardant colored paper; wherein: the coating adopted by the surface coating process is flame-retardant styrene-acrylic latex.
3. The method for preparing the high-strength water-resistant flame-retardant pigmented paper according to claim 2, characterized in that: the mass ratio of the slurry fiber to the flame-retardant styrene-acrylic latex is 1: 0.005-0.01.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010587187.5A CN111794012B (en) | 2020-06-24 | 2020-06-24 | High-strength water-resistant flame-retardant plain colored paper and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010587187.5A CN111794012B (en) | 2020-06-24 | 2020-06-24 | High-strength water-resistant flame-retardant plain colored paper and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111794012A CN111794012A (en) | 2020-10-20 |
| CN111794012B true CN111794012B (en) | 2022-04-29 |
Family
ID=72803768
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010587187.5A Active CN111794012B (en) | 2020-06-24 | 2020-06-24 | High-strength water-resistant flame-retardant plain colored paper and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111794012B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114032706B (en) * | 2021-11-18 | 2022-09-16 | 杭州中润华源装饰材料有限公司 | Heat-resistant flame-retardant decorative paper and preparation method thereof |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102225982B (en) * | 2011-05-06 | 2013-08-28 | 华南理工大学 | Miniemulsion polymerization method of high-solid-content self-crosslinking type styrene-acrylate emulsion surface sizing agent |
| CN103224579B (en) * | 2013-04-03 | 2014-04-02 | 华东理工大学 | Method of preparing low-molecular-weight styrene-acrylate emulsion copolymer |
| CN104387521B (en) * | 2014-11-27 | 2016-08-17 | 武汉工程大学 | A kind of montmorillonite and the preparation method of methacrylic acid compound modified acrylic ester core-shell emulsion |
| CN105294911A (en) * | 2015-11-30 | 2016-02-03 | 桂林市和鑫防水装饰材料有限公司 | Preparation method of styrene-butyl acrylate/montmorillonoid composite emulsion |
| CN106117406B (en) * | 2016-06-28 | 2019-02-12 | 合众（佛山）化工有限公司 | A kind of self-flame-retardant modifying cinepazid emulsion and preparation method thereof |
| CN108130808B (en) * | 2017-12-18 | 2020-04-28 | 佛山市板缘装饰材料有限公司 | Veneering decorative paper with flame-retardant effect and flame-retardant veneering artificial board adopting same |
| CN108795208B (en) * | 2018-07-15 | 2020-12-18 | 烟台大学 | Preparation method of flame-retardant water-based core-shell acrylate resin coating and paint |
| CN109881528B (en) * | 2019-03-15 | 2020-09-01 | 杭州华旺新材料科技股份有限公司 | Flame-retardant decorative base paper prepared from flame-retardant plant fibers and preparation method thereof |
-
2020
- 2020-06-24 CN CN202010587187.5A patent/CN111794012B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN111794012A (en) | 2020-10-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100580046C (en) | Starch-based aqueous macromolecule-isocyanate wood adhesive and preparation method thereof | |
| CN111205400B (en) | Low-internal-stress acrylic emulsion and preparation method thereof | |
| CN102776802B (en) | Reinforcing agent for papermaking and preparation method thereof | |
| EP2398831B1 (en) | Aqueous polymer dispersion made of a vinylaromatic compound, conjugated aliphatic diene, and ethylenically unsaturated acid | |
| CN109881528B (en) | Flame-retardant decorative base paper prepared from flame-retardant plant fibers and preparation method thereof | |
| EP3951049B1 (en) | High-performance environment-friendly kraft liner board, and preparation method thereof | |
| CN111533840B (en) | Environment-friendly water-resistant reinforced latex for paper and preparation method and application thereof | |
| CN108004841A (en) | A kind of Cypres and preparation method thereof | |
| CN111676728B (en) | Natural-color high-stiffness high-water-resistance raw paper for straw and preparation method thereof | |
| CN111794012B (en) | High-strength water-resistant flame-retardant plain colored paper and preparation method thereof | |
| CN104311716A (en) | Organic silicon modified styrene-acrylate microemulsion reinforcing agent as well as preparation method and application thereof | |
| EP1846524A1 (en) | Use of an aqueous polymer dispersion as a binding agent for cellulose fibers and for the production of filter materials | |
| EP2595841A1 (en) | Anti-drumming compound comprising emulsion polymer stabilized by protective colloid | |
| CN112724884A (en) | Styrene-acrylic emulsion plate alignment adhesive with long activation period and preparation method thereof | |
| EP0221400A1 (en) | Cationic paper-sizing agents | |
| CN106367830A (en) | Preparation method of flame-retardant regenerated cellulose fibers | |
| CN109705257B (en) | Humidity-adjusting acrylic emulsion and preparation method thereof | |
| CN106750255A (en) | A kind of preparation method and applications of anionic and nonionic type reactive emulsifier | |
| EP2555917B1 (en) | Use of synthetic adhesives for producing corrugated cardboard | |
| CN106188402B (en) | A kind of waterborne epoxy modified acrylic lotion and preparation method thereof | |
| CN103334339B (en) | Positive ion styrene-acrylic emulsion surface sizing agent with high reactivity for papermaking and synthetic method thereof | |
| CN105541125A (en) | Modification method for enhancing flexibility of brucite fiber | |
| US4378446A (en) | Acrylate-modified melamine resin which is stable on storage, its preparation and its use | |
| CN109293834A (en) | A kind of preparation method of styrene-butadiene latex and products thereof and application | |
| CN1861680A (en) | Low fluorine content material and synthesizing process thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |