CN113026413A - Flame-retardant impregnated paper and preparation method thereof - Google Patents

Flame-retardant impregnated paper and preparation method thereof Download PDF

Info

Publication number
CN113026413A
CN113026413A CN202110263453.3A CN202110263453A CN113026413A CN 113026413 A CN113026413 A CN 113026413A CN 202110263453 A CN202110263453 A CN 202110263453A CN 113026413 A CN113026413 A CN 113026413A
Authority
CN
China
Prior art keywords
weight
parts
flame
retardant
solution
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202110263453.3A
Other languages
Chinese (zh)
Inventor
朱雪男
杜永良
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tianjin Shengshide New Material Technology Co ltd
Original Assignee
Tianjin Shengshide New Material Technology Co ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Tianjin Shengshide New Material Technology Co ltd filed Critical Tianjin Shengshide New Material Technology Co ltd
Priority to CN202110263453.3A priority Critical patent/CN113026413A/en
Publication of CN113026413A publication Critical patent/CN113026413A/en
Pending legal-status Critical Current

Links

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
    • 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
    • D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/47—Condensation polymers of aldehydes or ketones
    • D21H17/49—Condensation polymers of aldehydes or ketones with compounds containing hydrogen bound to nitrogen
    • D21H17/51—Triazines, e.g. melamine
    • 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
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
    • C08G12/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
    • C08G12/34—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds and acyclic or carbocyclic compounds
    • C08G12/36—Ureas; Thioureas
    • C08G12/38—Ureas; Thioureas and melamines
    • 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
    • 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
    • D21H21/34—Ignifugeants

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Paper (AREA)
  • Phenolic Resins Or Amino Resins (AREA)

Abstract

The invention relates to flame-retardant impregnated paper and a preparation method thereof, wherein the flame-retardant impregnated paper comprises base paper, a matrix resin colloid and a flame-retardant impregnated colloid, wherein the matrix resin colloid comprises the following raw materials: formaldehyde solution, urea, melamine, hexamethylenetetramine, sodium hydroxide solution and ammonium chloride solution; the flame-retardant impregnating colloid is prepared from a solution B and a solution A, wherein the solution A comprises the following raw materials: potassium persulfate and deionized water; the raw materials of the solution B comprise: deionized water, acrylic acid, butyl acrylate, methyl methacrylate, hydroxyethyl methacrylate phosphate, sodium dodecyl sulfate and nonylphenol polyoxyethylene ether. Compared with the prior art, according to the flame-retardant impregnated paper disclosed by the embodiment of the invention, the viscosity of the matrix resin colloid is not less than 22.58mPa & s at 20 ℃, the solid content is not less than 48.58%, and the free formaldehyde content is not more than 0.28%; the prepared flame-retardant impregnated paper can reach the flame-retardant grade B1 (B).

Description

Flame-retardant impregnated paper and preparation method thereof
Technical Field
The invention belongs to the field of impregnated paper, and particularly relates to flame-retardant impregnated paper and a preparation method thereof.
Background
In recent years, artificial floors are increasingly popular in the market due to their characteristics of beauty and light weight, and are more and more widely applied to the fields of civil residential buildings and public buildings. The artificial floor is made of various base papers made of different materials through impregnation treatment and compounding and superposition, and the impregnated paper is the most important component of the artificial floor. In actual production, manufacture and application, impregnated paper still has many aspects to be improved, wherein how to improve the manufacturing efficiency and improve the storability, mechanical property, wear resistance, corrosion resistance, high and low temperature resistance and environmental protection performance of impregnated paper on the basis of reducing the cost of raw materials and processes is the focus of research in the field of impregnated paper. With the continuous improvement of safety consciousness of people, the application end, especially the fields of high-rise buildings and the like, puts forward the flame retardant requirement on the impregnated paper. In order to meet the requirement of flame retardant grade in the application field, the conventional flame retardant modification mode of the impregnated paper mainly comprises the steps of blending, fiber compounding and microcapsule filling of the impregnating colloid, so that the impregnated paper has flame retardant property. The above treatment method has the following defects: 1) the modes of blending, fiber compounding and microcapsule filling can reduce the viscosity of the impregnating colloid and the basic performances of curing and the like; 2) the uniform distribution of various composite flame-retardant phases greatly increases the process cost; 3) in order to facilitate the implementation of flame retardant modification, other modification spaces of the matrix resin are compressed, which is not favorable for the environmental performance of the impregnated colloid and the impregnated paper.
Disclosure of Invention
The invention provides flame-retardant impregnated paper and a preparation method thereof, and the main points of the invention are as follows:
according to an aspect of the present invention, a flame retardant impregnated paper comprises base paper, a matrix resin colloid and a flame retardant impregnated colloid, wherein the matrix resin colloid comprises the following raw materials: 100 parts by weight of formaldehyde solution, 71-88 parts by weight of urea, 7 parts by weight of melamine, 0.25 part by weight of hexamethylenetetramine, sodium hydroxide solution and ammonium chloride solution; the flame-retardant impregnating colloid is prepared from 100 parts by weight of solution B, 10-30 parts by weight of solution A and ammonia water, wherein the solution A comprises the following raw materials: 2.2 parts by weight of potassium persulfate and 150 parts by weight of deionized water; the raw materials of the solution B comprise: 200 parts of deionized water, 0.5-0.8 part of acrylic acid, 100 parts of butyl acrylate, 115 parts of methyl methacrylate, 9-36 parts of hydroxyethyl methacrylate phosphate, 1.5 parts of sodium dodecyl sulfate and 3 parts of nonylphenol polyoxyethylene ether.
According to another aspect of the present invention, there is provided a method for preparing a flame retardant impregnated paper, comprising the steps of:
first, preparation of matrix resin colloid
1) Adding 100 parts by weight of 39% formaldehyde solution, 28-33 parts by weight of first urea and 3.3 parts by weight of first melamine into a reaction kettle; adjusting the pH value of the reaction system to 8.0 by adopting 0.1mol/L sodium hydroxide solution, heating to 80 ℃, and reacting for 30 min;
2) adjusting the pH value of the reaction system to 4.8 by adopting 0.1mol/L ammonium chloride solution, heating to 90 ℃, and continuing to react for 15 min;
3) adjusting the pH value of a reaction system to 5.2 by adopting 0.1mol/L sodium hydroxide solution, adding 20-25 parts by weight of second batch of urea and 2.5 parts by weight of second batch of melamine into a reaction kettle according to the weight part ratio, and reacting for 30min at 90 ℃;
4) adjusting the pH value of a reaction system to 6.6 by adopting 0.1mol/L sodium hydroxide solution, adding 15-18 parts by weight of third batch of urea and 1.2 parts by weight of third batch of melamine into a reaction kettle according to the weight part ratio, and reacting for 30min at 90 ℃;
5) cooling to 75 ℃, adding 8-12 parts by weight of fourth batch of urea and 0.25 part by weight of hexamethylenetetramine, reacting for 15-25min at 55 ℃, cooling and discharging to obtain matrix resin colloid;
preparation of flame-retardant impregnating colloid
1) Preparing 2.2 parts by weight of potassium persulfate and 150 parts by weight of deionized water into a solution A for later use according to the weight part ratio;
2) preparing 200 parts by weight of deionized water, 0.5-0.8 part by weight of acrylic acid, 100 parts by weight of butyl acrylate, 115 parts by weight of methyl methacrylate, 9-36 parts by weight of hydroxyethyl methacrylate phosphate, 1.5 parts by weight of sodium dodecyl sulfate and 3 parts by weight of nonylphenol polyoxyethylene ether into a solution B for later use;
3) adding 100 parts by weight of the solution B into a reaction kettle, stirring and heating to 80 ℃, adding 10-30 parts by weight of the solution A, and keeping the temperature for 30 min; heating to 85 ℃, keeping the temperature for 45min, stirring and cooling to 40 ℃, adjusting the pH value of a reaction system to 7-8 by using ammonia water with the concentration of 0.1mol/L, and filtering to obtain a flame-retardant impregnating colloid for later use;
third, dipping treatment
1) Pretreating the base paper under the conditions of vacuum negative pressure of 0.05MPa and 60 ℃;
2) pre-impregnating matrix resin colloid: under the conditions of 0.05MPa vacuum pressure and 35 ℃, dipping the pretreated base paper in matrix resin colloid to obtain pre-impregnated paper;
3) pre-impregnating with flame-retardant impregnating colloid: dipping the pre-impregnated paper into the flame-retardant dipping colloid to obtain flame-retardant pre-impregnated paper;
4) supercritical drying and forming: immersing the flame-retardant impregnated paper into a supercritical dryer storing ethanol, reducing the temperature in the supercritical dryer to-5 ℃, and introducing liquid CO2And (4) performing supercritical treatment to obtain the flame-retardant impregnated paper.
According to an exemplary embodiment of the present invention, the impregnation amount of the matrix resin colloid pre-impregnation treatment is 15g/m2-22g/m2。
According to an exemplary embodiment of the present invention, the impregnating amount of the flame retardant impregnating colloid pre-impregnation treatment is 5g/m2-12g/m2。
According to an exemplary embodiment of the present invention, the vacuum pressure of the supercritical process is 0.15MPa, and the process time is 25 min.
According to an exemplary embodiment of the present invention, the viscosity of the matrix resin colloid is not less than 22.58 mPa-s, the solid content is not less than 48.58%, and the free formaldehyde content is less than 0.3%.
Compared with the prior art, according to the flame-retardant impregnated paper provided by the embodiment of the invention, base resin colloid and flame-retardant impregnated colloid are adopted to impregnate and form base paper, wherein the viscosity of the base resin colloid is not less than 22.58mPa & s at 20 ℃, the solid content is not less than 48.58%, and the free formaldehyde content is not more than 0.28%; the prepared flame-retardant impregnated paper can reach the flame-retardant grade B1 (B).
Detailed Description
In order to make the technical solution and advantages of the present invention more apparent, the present invention is further described in detail by the following specific examples. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
Example 1: preparation of flame-retardant impregnated paper
First, preparation of matrix resin colloid
1) Adding 100 parts by weight of 39% formaldehyde solution, 28 parts by weight of first urea and 3.3 parts by weight of first melamine into a reaction kettle; adjusting the pH value of the reaction system to 8.0 by adopting 0.1mol/L sodium hydroxide solution, heating to 80 ℃, and reacting for 30 min;
2) adjusting the pH value of the reaction system to 4.8 by adopting 0.1mol/L ammonium chloride solution, heating to 90 ℃, and continuing to react for 15 min;
3) adjusting the pH value of a reaction system to 5.2 by adopting 0.1mol/L sodium hydroxide solution, adding 25 parts by weight of second urea and 2.5 parts by weight of second melamine into a reaction kettle according to the weight part ratio, and reacting for 30min at 90 ℃;
4) adjusting the pH value of a reaction system to 6.6 by adopting 0.1mol/L sodium hydroxide solution, adding 18 parts by weight of third batch of urea and 1.2 parts by weight of third batch of melamine into a reaction kettle according to the weight part ratio, and reacting for 30min at 90 ℃;
5) cooling to 75 ℃, adding 8 parts by weight of fourth batch of urea and 0.25 part by weight of hexamethylenetetramine, reacting for 15min at 55 ℃, cooling and discharging to obtain matrix resin colloid;
preparation of flame-retardant impregnating colloid
1) Preparing 2.2 parts by weight of potassium persulfate and 150 parts by weight of deionized water into a solution A for later use according to the weight part ratio;
2) preparing 200 parts by weight of deionized water, 0.5 part by weight of acrylic acid, 100 parts by weight of butyl acrylate, 115 parts by weight of methyl methacrylate, 9 parts by weight of hydroxyethyl methacrylate phosphate, 1.5 parts by weight of sodium dodecyl sulfate and 3 parts by weight of nonylphenol polyoxyethylene ether into a solution B for later use;
3) adding 100 parts by weight of the solution B into a reaction kettle, stirring and heating to 80 ℃, adding 10 parts by weight of the solution A, and keeping the temperature for 30 min; heating to 85 ℃, keeping the temperature for 45min, stirring and cooling to 40 ℃, adjusting the pH value of a reaction system to 7-8 by using ammonia water with the concentration of 0.1mol/L, and filtering to obtain a flame-retardant impregnating colloid for later use;
third, dipping treatment
1) Pretreating the base paper under the conditions of vacuum negative pressure of 0.05MPa and 60 ℃;
2) pre-impregnating matrix resin colloid: under the conditions of 0.05MPa vacuum pressure and 35 ℃, the pretreated base paper is soaked in matrix resin colloid, and the soaking amount is 15g/m2-22g/m2Obtaining pre-impregnated paper;
3) pre-impregnating with flame-retardant impregnating colloid: the pre-impregnated paper is dipped into the flame-retardant dipping colloid, and the dipping amount is 5g/m2-12g/m2Obtaining flame-retardant pre-impregnated paper;
4) supercritical drying and forming: immersing the flame-retardant impregnated paper into a supercritical dryer storing ethanol, reducing the temperature in the supercritical dryer to-5 ℃, and introducing liquid CO2And (4) performing supercritical treatment, wherein the vacuum pressure of the supercritical treatment is 0.15MPa, and the treatment time is 25min, so as to obtain the flame-retardant impregnated paper.
The sample according to this example has a solids content of 52.29%, a viscosity of 23.52 mPas at 20 ℃ and a free formaldehyde content of 0.26%.
Example 2: preparation of flame-retardant impregnated paper
First, preparation of matrix resin colloid
1) Adding 100 parts by weight of 39% formaldehyde solution, 30 parts by weight of first urea and 3.3 parts by weight of first melamine into a reaction kettle; adjusting the pH value of the reaction system to 8.0 by adopting 0.1mol/L sodium hydroxide solution, heating to 80 ℃, and reacting for 30 min;
2) adjusting the pH value of the reaction system to 4.8 by adopting 0.1mol/L ammonium chloride solution, heating to 90 ℃, and continuing to react for 15 min;
3) adjusting the pH value of a reaction system to 5.2 by adopting 0.1mol/L sodium hydroxide solution, adding 24 parts by weight of second urea and 2.5 parts by weight of second melamine into a reaction kettle according to the weight part ratio, and reacting for 30min at 90 ℃;
4) adjusting the pH value of a reaction system to 6.6 by adopting 0.1mol/L sodium hydroxide solution, adding 18 parts by weight of third batch of urea and 1.2 parts by weight of third batch of melamine into a reaction kettle according to the weight part ratio, and reacting for 30min at 90 ℃;
5) cooling to 75 ℃, adding 9 parts by weight of fourth batch of urea and 0.25 part by weight of hexamethylenetetramine, reacting for 20min at 55 ℃, cooling and discharging to obtain matrix resin colloid;
preparation of flame-retardant impregnating colloid
1) Preparing 2.2 parts by weight of potassium persulfate and 150 parts by weight of deionized water into a solution A for later use according to the weight part ratio;
2) preparing 200 parts by weight of deionized water, 0.5 part by weight of acrylic acid, 100 parts by weight of butyl acrylate, 115 parts by weight of methyl methacrylate, 15 parts by weight of hydroxyethyl methacrylate phosphate, 1.5 parts by weight of sodium dodecyl sulfate and 3 parts by weight of nonylphenol polyoxyethylene ether into a solution B for later use;
3) adding 100 parts by weight of the solution B into a reaction kettle, stirring and heating to 80 ℃, adding 15 parts by weight of the solution A, and keeping the temperature for 30 min; heating to 85 ℃, keeping the temperature for 45min, stirring and cooling to 40 ℃, adjusting the pH value of a reaction system to 7-8 by using ammonia water with the concentration of 0.1mol/L, and filtering to obtain a flame-retardant impregnating colloid for later use;
third, dipping treatment
1) Pretreating the base paper under the conditions of vacuum negative pressure of 0.05MPa and 60 ℃;
2) pre-impregnating matrix resin colloid: under the conditions of 0.05MPa vacuum pressure and 35 ℃, the pretreated base paper is soaked in matrix resin colloid, and the soaking amount is 15g/m2-22g/m2Obtaining pre-impregnated paper;
3) pre-impregnating with flame-retardant impregnating colloid: the pre-impregnated paper is dipped into the flame-retardant dipping colloid, and the dipping amount is 5g/m2-12g/m2Obtaining flame-retardant pre-impregnated paper;
4) supercritical drying and forming: immersing the flame-retardant impregnated paper into a supercritical dryer storing ethanol, reducing the temperature in the supercritical dryer to-5 ℃, and introducing liquid CO2And (4) performing supercritical treatment, wherein the vacuum pressure of the supercritical treatment is 0.15MPa, and the treatment time is 25min, so as to obtain the flame-retardant impregnated paper.
The sample according to this example has a solids content of 48.58%, a viscosity of 22.82 mPas at 20 ℃ and a free formaldehyde content of 0.25%.
Example 3: preparation of flame-retardant impregnated paper
First, preparation of matrix resin colloid
1) Adding 100 parts by weight of 39% formaldehyde solution, 30 parts by weight of first urea and 3.3 parts by weight of first melamine into a reaction kettle; adjusting the pH value of the reaction system to 8.0 by adopting 0.1mol/L sodium hydroxide solution, heating to 80 ℃, and reacting for 30 min;
2) adjusting the pH value of the reaction system to 4.8 by adopting 0.1mol/L ammonium chloride solution, heating to 90 ℃, and continuing to react for 15 min;
3) adjusting the pH value of a reaction system to 5.2 by adopting 0.1mol/L sodium hydroxide solution, adding 23 parts by weight of second urea and 2.5 parts by weight of second melamine into a reaction kettle according to the weight part ratio, and reacting for 30min at 90 ℃;
4) adjusting the pH value of a reaction system to 6.6 by adopting 0.1mol/L sodium hydroxide solution, adding 17 parts by weight of third batch of urea and 1.2 parts by weight of third batch of melamine into a reaction kettle according to the weight part ratio, and reacting for 30min at 90 ℃;
5) cooling to 75 ℃, adding 10 parts by weight of fourth batch of urea and 0.25 part by weight of hexamethylenetetramine, reacting for 20min at 55 ℃, cooling and discharging to obtain matrix resin colloid;
preparation of flame-retardant impregnating colloid
1) Preparing 2.2 parts by weight of potassium persulfate and 150 parts by weight of deionized water into a solution A for later use according to the weight part ratio;
2) preparing 200 parts by weight of deionized water, 0.6 part by weight of acrylic acid, 100 parts by weight of butyl acrylate, 115 parts by weight of methyl methacrylate, 22 parts by weight of hydroxyethyl methacrylate phosphate, 1.5 parts by weight of sodium dodecyl sulfate and 3 parts by weight of nonylphenol polyoxyethylene ether into a solution B for later use;
3) adding 100 parts by weight of the solution B into a reaction kettle, stirring and heating to 80 ℃, adding 19 parts by weight of the solution A, and keeping the temperature for 30 min; heating to 85 ℃, keeping the temperature for 45min, stirring and cooling to 40 ℃, adjusting the pH value of a reaction system to 7-8 by using ammonia water with the concentration of 0.1mol/L, and filtering to obtain a flame-retardant impregnating colloid for later use;
third, dipping treatment
1) Pretreating the base paper under the conditions of vacuum negative pressure of 0.05MPa and 60 ℃;
2) pre-impregnating matrix resin colloid: under the conditions of 0.05MPa vacuum pressure and 35 ℃, the pretreated base paper is soaked in matrix resin colloid, and the soaking amount is 15g/m2-22g/m2Obtaining pre-impregnated paper;
3) pre-impregnating with flame-retardant impregnating colloid: the pre-impregnated paper is dipped into the flame-retardant dipping colloid, and the dipping amount is 5g/m2-12g/m2Obtaining flame-retardant pre-impregnated paper;
4) supercritical drying and forming: immersing the flame-retardant impregnated paper into a supercritical dryer with ethanol stored therein, and then supercedingThe temperature in the boundary drier is reduced to-5 ℃, and liquid CO is introduced2And (4) performing supercritical treatment, wherein the vacuum pressure of the supercritical treatment is 0.15MPa, and the treatment time is 25min, so as to obtain the flame-retardant impregnated paper.
The sample according to this example had a solids content of 49.22%, a viscosity of 26.15 mPas at 20 ℃ and a free formaldehyde content of 0.25%.
Example 4: preparation of flame-retardant impregnated paper
First, preparation of matrix resin colloid
1) Adding 100 parts by weight of 39% formaldehyde solution, 31 parts by weight of first urea and 3.3 parts by weight of first melamine into a reaction kettle; adjusting the pH value of the reaction system to 8.0 by adopting 0.1mol/L sodium hydroxide solution, heating to 80 ℃, and reacting for 30 min;
2) adjusting the pH value of the reaction system to 4.8 by adopting 0.1mol/L ammonium chloride solution, heating to 90 ℃, and continuing to react for 15 min;
3) adjusting the pH value of a reaction system to 5.2 by adopting 0.1mol/L sodium hydroxide solution, adding 22 parts by weight of second urea and 2.5 parts by weight of second melamine into a reaction kettle according to the weight part ratio, and reacting for 30min at 90 ℃;
4) adjusting the pH value of a reaction system to 6.6 by adopting 0.1mol/L sodium hydroxide solution, adding 16 parts by weight of third batch of urea and 1.2 parts by weight of third batch of melamine into a reaction kettle according to the weight part ratio, and reacting for 30min at 90 ℃;
5) cooling to 75 ℃, adding 11 parts by weight of fourth batch of urea and 0.25 part by weight of hexamethylenetetramine, reacting for 25min at 55 ℃, cooling and discharging to obtain matrix resin colloid;
preparation of flame-retardant impregnating colloid
1) Preparing 2.2 parts by weight of potassium persulfate and 150 parts by weight of deionized water into a solution A for later use according to the weight part ratio;
2) preparing 200 parts by weight of deionized water, 0.7 part by weight of acrylic acid, 100 parts by weight of butyl acrylate, 115 parts by weight of methyl methacrylate, 28 parts by weight of hydroxyethyl methacrylate phosphate, 1.5 parts by weight of sodium dodecyl sulfate and 3 parts by weight of nonylphenol polyoxyethylene ether into a solution B for later use;
3) adding 100 parts by weight of the solution B into a reaction kettle, stirring and heating to 80 ℃, adding 24 parts by weight of the solution A, and keeping the temperature for 30 min; heating to 85 ℃, keeping the temperature for 45min, stirring and cooling to 40 ℃, adjusting the pH value of a reaction system to 7-8 by using ammonia water with the concentration of 0.1mol/L, and filtering to obtain a flame-retardant impregnating colloid for later use;
third, dipping treatment
1) Pretreating the base paper under the conditions of vacuum negative pressure of 0.05MPa and 60 ℃;
2) pre-impregnating matrix resin colloid: under the conditions of 0.05MPa vacuum pressure and 35 ℃, the pretreated base paper is soaked in matrix resin colloid, and the soaking amount is 15g/m2-22g/m2Obtaining pre-impregnated paper;
3) pre-impregnating with flame-retardant impregnating colloid: the pre-impregnated paper is dipped into the flame-retardant dipping colloid, and the dipping amount is 5g/m2-12g/m2Obtaining flame-retardant pre-impregnated paper;
4) supercritical drying and forming: immersing the flame-retardant impregnated paper into a supercritical dryer storing ethanol, reducing the temperature in the supercritical dryer to-5 ℃, and introducing liquid CO2And (4) performing supercritical treatment, wherein the vacuum pressure of the supercritical treatment is 0.15MPa, and the treatment time is 25min, so as to obtain the flame-retardant impregnated paper.
The sample according to this example has a solids content of 55.18%, a viscosity of 28.39 mPas at 20 ℃ and a free formaldehyde content of 0.25%.
Example 5: preparation of flame-retardant impregnated paper
First, preparation of matrix resin colloid
1) Adding 100 parts by weight of 39% formaldehyde solution, 33 parts by weight of first urea and 3.3 parts by weight of first melamine into a reaction kettle; adjusting the pH value of the reaction system to 8.0 by adopting 0.1mol/L sodium hydroxide solution, heating to 80 ℃, and reacting for 30 min;
2) adjusting the pH value of the reaction system to 4.8 by adopting 0.1mol/L ammonium chloride solution, heating to 90 ℃, and continuing to react for 15 min;
3) adjusting the pH value of a reaction system to 5.2 by adopting 0.1mol/L sodium hydroxide solution, adding 20 parts by weight of second urea and 2.5 parts by weight of second melamine into a reaction kettle according to the weight part ratio, and reacting for 30min at 90 ℃;
4) adjusting the pH value of a reaction system to 6.6 by adopting 0.1mol/L sodium hydroxide solution, adding 15 parts by weight of third batch of urea and 1.2 parts by weight of third batch of melamine into a reaction kettle according to the weight part ratio, and reacting for 30min at 90 ℃;
5) cooling to 75 ℃, adding 12 parts by weight of fourth batch of urea and 0.25 part by weight of hexamethylenetetramine, reacting for 25min at 55 ℃, cooling and discharging to obtain matrix resin colloid;
preparation of flame-retardant impregnating colloid
1) Preparing 2.2 parts by weight of potassium persulfate and 150 parts by weight of deionized water into a solution A for later use according to the weight part ratio;
2) preparing 200 parts by weight of deionized water, 0.8 part by weight of acrylic acid, 100 parts by weight of butyl acrylate, 115 parts by weight of methyl methacrylate, 36 parts by weight of hydroxyethyl methacrylate phosphate, 1.5 parts by weight of sodium dodecyl sulfate and 3 parts by weight of nonylphenol polyoxyethylene ether into solution B for later use;
3) adding 100 parts by weight of the solution B into a reaction kettle, stirring and heating to 80 ℃, adding 30 parts by weight of the solution A, and keeping the temperature for 30 min; heating to 85 ℃, keeping the temperature for 45min, stirring and cooling to 40 ℃, adjusting the pH value of a reaction system to 7-8 by using ammonia water with the concentration of 0.1mol/L, and filtering to obtain a flame-retardant impregnating colloid for later use;
third, dipping treatment
1) Pretreating the base paper under the conditions of vacuum negative pressure of 0.05MPa and 60 ℃;
2) pre-impregnating matrix resin colloid: under the conditions of 0.05MPa vacuum pressure and 35 ℃, the pretreated base paper is soaked in matrix resin colloid, and the soaking amount is 15g/m2-22g/m2Obtaining pre-impregnated paper;
3) pre-impregnating with flame-retardant impregnating colloid: impregnating the preimpregnated paper in flame-retardant impregnationThe impregnation amount in the impregnation colloid is 5g/m2-12g/m2Obtaining flame-retardant pre-impregnated paper;
4) supercritical drying and forming: immersing the flame-retardant impregnated paper into a supercritical dryer storing ethanol, reducing the temperature in the supercritical dryer to-5 ℃, and introducing liquid CO2And (4) performing supercritical treatment, wherein the vacuum pressure of the supercritical treatment is 0.15MPa, and the treatment time is 25min, so as to obtain the flame-retardant impregnated paper.
The sample according to this example has a solids content of 53.85%, a viscosity of 22.58 mPas at 20 ℃ and a free formaldehyde content of 0.28%.
Example 6:
flammability tests were carried out on the flame-retardant impregnated papers prepared in examples 1 to 5 according to GB/T8626-2007 flammability test methods for building materials.
TABLE 1
Figure BDA0002971053790000091
From Table 1, the flame-retardant impregnated papers prepared in examples 1 to 5 achieved a flame retardancy grade B1(B) according to GB/T8624-.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are merely exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (6)

1. The flame-retardant impregnated paper is characterized by comprising base paper, a matrix resin colloid and a flame-retardant impregnated colloid, wherein the matrix resin colloid comprises the following raw materials: 100 parts by weight of formaldehyde solution, 71-88 parts by weight of urea, 7 parts by weight of melamine, 0.25 part by weight of hexamethylenetetramine, sodium hydroxide solution and ammonium chloride solution; the flame-retardant impregnating colloid is prepared from 100 parts by weight of solution B, 10-30 parts by weight of solution A and ammonia water, wherein the solution A comprises the following raw materials: 2.2 parts by weight of potassium persulfate and 150 parts by weight of deionized water; the raw materials of the solution B comprise: 200 parts of deionized water, 0.5-0.8 part of acrylic acid, 100 parts of butyl acrylate, 115 parts of methyl methacrylate, 9-36 parts of hydroxyethyl methacrylate phosphate, 1.5 parts of sodium dodecyl sulfate and 3 parts of nonylphenol polyoxyethylene ether.
2. A method of making flame retardant impregnated paper, the method comprising:
first, preparation of matrix resin colloid
1) Adding 100 parts by weight of 39% formaldehyde solution, 28-33 parts by weight of first urea and 3.3 parts by weight of first melamine into a reaction kettle; adjusting the pH value of the reaction system to 8.0 by adopting 0.1mol/L sodium hydroxide solution, heating to 80 ℃, and reacting for 30 min;
2) adjusting the pH value of the reaction system to 4.8 by adopting 0.1mol/L ammonium chloride solution, heating to 90 ℃, and continuing to react for 15 min;
3) adjusting the pH value of a reaction system to 5.2 by adopting 0.1mol/L sodium hydroxide solution, adding 20-25 parts by weight of second batch of urea and 2.5 parts by weight of second batch of melamine into a reaction kettle according to the weight part ratio, and reacting for 30min at 90 ℃;
4) adjusting the pH value of a reaction system to 6.6 by adopting 0.1mol/L sodium hydroxide solution, adding 15-18 parts by weight of third batch of urea and 1.2 parts by weight of third batch of melamine into a reaction kettle according to the weight part ratio, and reacting for 30min at 90 ℃;
5) cooling to 75 ℃, adding 8-12 parts by weight of fourth batch of urea and 0.25 part by weight of hexamethylenetetramine, reacting for 15-25min at 55 ℃, cooling and discharging to obtain matrix resin colloid;
preparation of flame-retardant impregnating colloid
1) Preparing 2.2 parts by weight of potassium persulfate and 150 parts by weight of deionized water into a solution A for later use according to the weight part ratio;
2) preparing 200 parts by weight of deionized water, 0.5-0.8 part by weight of acrylic acid, 100 parts by weight of butyl acrylate, 115 parts by weight of methyl methacrylate, 9-36 parts by weight of hydroxyethyl methacrylate phosphate, 1.5 parts by weight of sodium dodecyl sulfate and 3 parts by weight of nonylphenol polyoxyethylene ether into a solution B for later use;
3) adding 100 parts by weight of the solution B into a reaction kettle, stirring and heating to 80 ℃, adding 10-30 parts by weight of the solution A, and keeping the temperature for 30 min; heating to 85 ℃, keeping the temperature for 45min, stirring and cooling to 40 ℃, adjusting the pH value of a reaction system to 7-8 by using ammonia water with the concentration of 0.1mol/L, and filtering to obtain a flame-retardant impregnating colloid for later use;
third, dipping treatment
1) Pretreating the base paper under the conditions of vacuum negative pressure of 0.05MPa and 60 ℃;
2) pre-impregnating matrix resin colloid: under the conditions of 0.05MPa vacuum pressure and 35 ℃, dipping the pretreated base paper in matrix resin colloid to obtain pre-impregnated paper;
3) pre-impregnating with flame-retardant impregnating colloid: dipping the pre-impregnated paper into the flame-retardant dipping colloid to obtain flame-retardant pre-impregnated paper;
4) supercritical drying and forming: immersing the flame-retardant impregnated paper into a supercritical dryer storing ethanol, reducing the temperature in the supercritical dryer to-5 ℃, and introducing liquid CO2And (4) performing supercritical treatment to obtain the flame-retardant impregnated paper.
3. The method of claim 2, wherein the impregnation amount of the matrix resin colloid pre-impregnation treatment is 15g/m2-22g/m2。
4. The method of claim 2, wherein the impregnating amount of the flame retardant impregnating colloid pre-impregnation treatment is 5g/m2-12 g/m2。
5. The method according to claim 2, wherein the vacuum pressure of the supercritical treatment is 0.15MPa, and the treatment time is 25 min.
6. The production method according to claim 2, wherein the viscosity of the matrix resin colloid is not less than 22.58 mPa-s, the solid content is not less than 48.58%, and the free formaldehyde content is not more than 0.28%.
CN202110263453.3A 2021-03-11 2021-03-11 Flame-retardant impregnated paper and preparation method thereof Pending CN113026413A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110263453.3A CN113026413A (en) 2021-03-11 2021-03-11 Flame-retardant impregnated paper and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110263453.3A CN113026413A (en) 2021-03-11 2021-03-11 Flame-retardant impregnated paper and preparation method thereof

Publications (1)

Publication Number Publication Date
CN113026413A true CN113026413A (en) 2021-06-25

Family

ID=76469580

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110263453.3A Pending CN113026413A (en) 2021-03-11 2021-03-11 Flame-retardant impregnated paper and preparation method thereof

Country Status (1)

Country Link
CN (1) CN113026413A (en)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070082194A1 (en) * 2003-07-28 2007-04-12 Ann Denholm Fire retardant paper
CN101591867A (en) * 2008-05-29 2009-12-02 任玉良 Melamine modified urea-formaldehyde resin used for dipping paper of decorative laminated plate and preparation method thereof
CN204738180U (en) * 2015-01-04 2015-11-04 成都建丰装饰纸有限公司 Fine definition is impregnated paper for furniture
CN106117476A (en) * 2016-08-04 2016-11-16 广西三威林产工业有限公司 High density fiberboard moistureproof adhesive and preparation method thereof
CN107815867A (en) * 2017-11-02 2018-03-20 桐乡市星邦科技发展有限公司 A kind of water-fastness anti-flaming function spinning coating water paste of Halogen and preparation method thereof
CN109537355A (en) * 2018-11-15 2019-03-29 天津市盛世德新材料科技有限公司 Long-acting no aldehyde impregnated paper and preparation method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070082194A1 (en) * 2003-07-28 2007-04-12 Ann Denholm Fire retardant paper
CN101591867A (en) * 2008-05-29 2009-12-02 任玉良 Melamine modified urea-formaldehyde resin used for dipping paper of decorative laminated plate and preparation method thereof
CN204738180U (en) * 2015-01-04 2015-11-04 成都建丰装饰纸有限公司 Fine definition is impregnated paper for furniture
CN106117476A (en) * 2016-08-04 2016-11-16 广西三威林产工业有限公司 High density fiberboard moistureproof adhesive and preparation method thereof
CN107815867A (en) * 2017-11-02 2018-03-20 桐乡市星邦科技发展有限公司 A kind of water-fastness anti-flaming function spinning coating water paste of Halogen and preparation method thereof
CN109537355A (en) * 2018-11-15 2019-03-29 天津市盛世德新材料科技有限公司 Long-acting no aldehyde impregnated paper and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
王潇霜等: "含磷丙烯酸树脂的制备及其阻燃性能研究", 《高效化学工程学报》 *

Similar Documents

Publication Publication Date Title
CN104985657B (en) Enhanced high-temperature heat treated wood and manufacturing method thereof
CN101100079B (en) Core-shell type multifunctional composite wood precursor solution and its preparation method
CN115091572A (en) Preparation method of environment-friendly high-strength flame-retardant decorative veneer
CN112300737A (en) Environment-friendly flame-retardant decorative paper
CN113858374B (en) Preparation method of biomass-based environment-friendly flame-retardant fiberboard
CN113026413A (en) Flame-retardant impregnated paper and preparation method thereof
CN107935433B (en) High-performance concrete sustained-release and controlled-release in-water curing material and preparation method thereof
CN117025002B (en) Fireproof flame-retardant composite board and preparation method thereof
CN103772640B (en) A kind of flame retardant type wood adhesive and its preparation method and application
CN117799026A (en) Composite silicon modified heat treatment method for wood
CN111944378A (en) Polymer-based waterproof film, preparation method and application thereof
CN106363732A (en) Furfuryl alcohol-added and phenolic resin-compounded fast-growing wood modifying agent
CN104786333A (en) Wood reinforced waterproof modification fluid and preparation method thereof
CN115849928B (en) Injection-molded aluminum oxide fiber reinforced composite material containing lanthanum phosphate interface layer and preparation method thereof
CN109537355B (en) Long-acting formaldehyde-free impregnated paper and preparation method thereof
CN109352776B (en) Method for improving performance of fast-growing wood by rosin-based unsaturated resin
CN114941204B (en) High-temperature-resistant flame-retardant heat-insulating cotton and processing technology thereof
CN106363738A (en) Composite flame retardant and waterproof modifying agent for modification of fast-growing wood for manufacturing outdoor furniture
CN113370335A (en) Organic-inorganic composite functional modified wood and processing technology
CN106625947A (en) Composite modifying agent added with oxide graphene modified emulsion for fast growing wood
CN116061279B (en) Modification treatment agent for in-situ reinforcing and toughening of wood and modification method thereof
CN111501339A (en) Composite material for wastewater treatment and preparation method thereof
CN110978181A (en) Method for improving performance of fast-growing wood by using bio-based rigid monomer
CN110258113A (en) A kind of processing method of antistatic underwear fabric
CN116694274B (en) Urea formaldehyde emulsion adhesive and preparation method 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
WD01 Invention patent application deemed withdrawn after publication
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20210625