CN113047078A - Formaldehyde purification ecological impregnated paper and preparation method thereof - Google Patents
Formaldehyde purification ecological impregnated paper and preparation method thereof Download PDFInfo
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- CN113047078A CN113047078A CN202110287651.3A CN202110287651A CN113047078A CN 113047078 A CN113047078 A CN 113047078A CN 202110287651 A CN202110287651 A CN 202110287651A CN 113047078 A CN113047078 A CN 113047078A
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
- D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
- D21H23/22—Addition to the formed paper
- D21H23/30—Pretreatment of the paper
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- 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
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/28—Chemically modified polycondensates
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- 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
- D21H19/24—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
- D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
- D21H23/22—Addition to the formed paper
- D21H23/32—Addition to the formed paper by contacting paper with an excess of material, e.g. from a reservoir or in a manner necessitating removal of applied excess material from the paper
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H25/00—After-treatment of paper not provided for in groups D21H17/00 - D21H23/00
- D21H25/04—Physical treatment, e.g. heating, irradiating
- D21H25/06—Physical treatment, e.g. heating, irradiating of impregnated or coated paper
Abstract
The invention relates to formaldehyde purification ecological impregnated paper and a preparation method thereof, wherein the formaldehyde purification ecological impregnated paper comprises base paper and modified matrix resin colloid which is impregnated and coated on the inner side and the outer side of the base paper, and the modified matrix resin colloid comprises the following raw materials: 80-150 parts of lignin extract, 150 parts of urea, 420 parts of formaldehyde solution, 50-150 parts of lignin gel microporous powder and 170 parts of sodium hydroxide solution; wherein, the raw materials of the lignin extracting solution comprise: 100 parts by weight of lignin, 500 parts by weight of hydrogen peroxide and 12 parts by weight of zinc chloride; the lignin gel microporous powder comprises the following raw materials: absolute ethyl alcohol, lignin, deionized water, an acetic acid solution and liquid nitrogen; the solid content of the modified matrix resin colloid is not less than 45%, and the viscosity at 20 ℃ is not less than 158 mPas.
Description
Technical Field
The invention belongs to the field of new materials, and particularly relates to formaldehyde purification ecological impregnated paper and a preparation method thereof.
Background
With the continuous and deep practice of the concept of promoting ecological livable life, the environmental protection and the promotion of the development of the green industry become important subjects of the current times. China is a large population country, and particularly, with the rapid development of economy, the building home decoration industry becomes an important economic component. But in line with this, it also puts a great strain on the environment and resource consumption. In order to reduce the consumption of original materials such as wood, bamboo and the like in the building home decoration industry, various artificial decorative materials such as artificial floors and the like are widely applied. The traditional artificial floor is prepared by impregnating raw paper with urea-formaldehyde resin or phenolic resin or polyurethane resin and then performing hot-pressing compounding or gluing on impregnated paper, and the impregnated paper inevitably releases formaldehyde and other harmful substances, wherein the urea-formaldehyde resin impregnation process is simple, the cost is low, the application proportion is maximum, and the release amount of formaldehyde is also maximum. With the continuous improvement of health and safety awareness of people, the requirement on the quality of the residential air is also continuously improved. Conventional impregnated paper products, particularly decorative materials for furniture manufacture and interior decoration, have become a major source of formaldehyde in the interior. How to avoid formaldehyde release of the impregnating resin and the impregnating paper in the using process is an important subject for protecting the health and safety of people and improving the living quality.
Disclosure of Invention
The invention provides formaldehyde purification ecological impregnated paper and a preparation method thereof, and the invention aims to provide the following steps:
according to one aspect of the invention, the formaldehyde-purifying ecological impregnated paper comprises base paper and modified matrix resin colloid which is impregnated and coated on the inner side and the outer side of the base paper, wherein the modified matrix resin colloid comprises the following raw materials: 80-150 parts of lignin extract, 150 parts of urea, 420 parts of formaldehyde solution, 50-150 parts of lignin gel microporous powder and 170 parts of sodium hydroxide solution; wherein, the raw materials of the lignin extracting solution comprise: 100 parts by weight of lignin, 500 parts by weight of hydrogen peroxide and 12 parts by weight of zinc chloride; the lignin gel microporous powder comprises the following raw materials: absolute ethyl alcohol, lignin, deionized water, an acetic acid solution and liquid nitrogen; the solid content of the modified matrix resin colloid is not less than 45%, and the viscosity at 20 ℃ is not less than 158 mPas.
According to another aspect of the present invention, a method for preparing formaldehyde-purified ecological impregnated paper, the method comprising:
first, preparation of lignin gel microporous powder
1) Preparation of lignin gel precursor solution
Adding lignin into absolute ethyl alcohol according to a solid-liquid ratio of 1:30, carrying out ultrasonic extraction at 35 ℃, and filtering to obtain a lignin extract; mixing 100 parts by weight of lignin extract and 300 parts by weight of deionized water according to the weight part ratio, stirring for 20min at the temperature of-5 ℃, adding 19 parts by weight of 0.15mol/L acetic acid solution into a reaction system, and carrying out ultrasonic treatment for 30min to obtain lignin gel precursor solution;
2) lignin wet gel preparation and purification treatment
Stirring the gel precursor solution at-2 deg.C for 180min, and standing for 12 hr to obtain lignin wet gel;
immersing the lignin wet gel into a supercritical purifier stored with absolute ethyl alcohol for purification treatment;
3) shaping process
Pre-cooling purified lignin wet gel at-15 deg.C for 3h, freezing in liquid nitrogen for 2min, pulverizing, and vacuum drying at 105 deg.C for 20min to obtain lignin gel microporous powder;
secondly, preparing lignin extracting solution
Uniformly mixing 100 parts by weight of lignin, 500 parts by weight of hydrogen peroxide with the mass fraction of 40% and 12 parts by weight of zinc chloride, reacting at the temperature of 180 ℃ for 80min, cooling to room temperature, and filtering to obtain a lignin extracting solution;
preparation of modified matrix resin colloid
1) Adding 80-150 parts by weight of lignin extracting solution, 20 parts by weight of first urea and 150 parts by weight of first formaldehyde solution into a reaction kettle according to the weight parts, and heating to 90 ℃ for reaction for 40 min;
2) adding 60 parts by weight of second urea, 120 parts by weight of second formaldehyde solution and 70 parts by weight of sodium hydroxide solution into a reaction system, and reacting at 85 ℃ for 60 min;
3) adding 150 parts by weight of a third batch of formaldehyde solution and 50 parts by weight of sodium hydroxide solution into the reaction system, and reacting for 60min at the temperature of 90 ℃;
4) adding 70 parts by weight of third batch of urea, 50-150 parts by weight of lignin gel microporous powder and 50 parts by weight of sodium hydroxide solution into a reaction system, stirring and reacting at 80 ℃ for 30min, cooling and discharging to obtain modified matrix resin colloid;
fourth, dipping treatment
1) Drying and pretreating the base paper at 50 ℃;
2) soaking the dried and pretreated base paper in the modified matrix resin adhesive at the temperature of 40 ℃ to obtain impregnated paper;
3) sequentially carrying out supercritical dryer treatment, presetting treatment and curing treatment on the impregnated paper; heating to 125 ℃, and treating for 25min to obtain the formaldehyde-purified ecological impregnated paper.
According to an exemplary embodiment of the present invention, the impregnation amount of the impregnation treatment is 15g/m2-35g/m2。
According to an exemplary embodiment of the present invention, the medium of the supercritical drying process is carbon dioxide, and the process temperature is-5 ℃.
According to an exemplary embodiment of the present invention, the pre-setting process is performed under a vacuum environment of 0.05MPa, a process temperature of 70 ℃, and a process time of 30 min.
According to an exemplary embodiment of the present invention, the curing process temperature is 125 ℃ and the process time is 25 min.
Compared with the prior art, the modified matrix resin colloid prepared according to the embodiment of the invention has the solid content of not less than 45% and the viscosity of not less than 158 mPa.s at 20 ℃, and the formaldehyde-purifying ecological impregnated paper prepared according to the embodiment of the invention does not contain free formaldehyde.
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 formaldehyde purification ecological impregnated paper
First, preparation of lignin gel microporous powder
1) Preparation of lignin gel precursor solution
Adding lignin into absolute ethyl alcohol according to a solid-liquid ratio of 1:30, carrying out ultrasonic extraction at 35 ℃, and filtering to obtain a lignin extract; mixing 100 parts by weight of lignin extract and 300 parts by weight of deionized water according to the weight part ratio, stirring for 20min at the temperature of-5 ℃, adding 19 parts by weight of 0.15mol/L acetic acid solution into a reaction system, and carrying out ultrasonic treatment for 30min to obtain lignin gel precursor solution;
2) lignin wet gel preparation and purification treatment
Stirring the gel precursor solution at-2 deg.C for 180min, and standing for 12 hr to obtain lignin wet gel;
immersing the lignin wet gel into a supercritical purifier stored with absolute ethyl alcohol for purification treatment;
3) shaping process
Pre-cooling purified lignin wet gel at-15 deg.C for 3h, freezing in liquid nitrogen for 2min, pulverizing, and vacuum drying at 105 deg.C for 20min to obtain lignin gel microporous powder;
secondly, preparing lignin extracting solution
Uniformly mixing 100 parts by weight of lignin, 500 parts by weight of hydrogen peroxide with the mass fraction of 40% and 12 parts by weight of zinc chloride, reacting at the temperature of 180 ℃ for 80min, cooling to room temperature, and filtering to obtain a lignin extracting solution;
preparation of modified matrix resin colloid
1) Adding 80 parts by weight of lignin extracting solution, 20 parts by weight of first urea and 150 parts by weight of first formaldehyde solution into a reaction kettle, and heating to 90 ℃ for reaction for 40 min;
2) adding 60 parts by weight of second urea, 120 parts by weight of second formaldehyde solution and 70 parts by weight of sodium hydroxide solution into a reaction system, and reacting at 85 ℃ for 60 min;
3) adding 150 parts by weight of a third batch of formaldehyde solution and 50 parts by weight of sodium hydroxide solution into the reaction system, and reacting for 60min at the temperature of 90 ℃;
4) adding 70 parts by weight of third batch of urea, 50 parts by weight of lignin gel microporous powder and 50 parts by weight of sodium hydroxide solution into a reaction system, stirring and reacting for 30min at 80 ℃, cooling and discharging to obtain modified matrix resin colloid;
fourth, dipping treatment
1) Drying and pretreating the base paper at 50 ℃;
2) soaking the dried and pretreated base paper in the modified matrix resin adhesive at the temperature of 40 ℃, wherein the soaking amount of the soaking treatment is 15g/m2-35g/m2Obtaining impregnated paper;
3) sequentially carrying out supercritical dryer treatment, pre-setting treatment and curing treatment on the impregnated paper, wherein the medium of the supercritical drying treatment is carbon dioxide, and the treatment temperature is-5 ℃; the pre-setting treatment is carried out under the vacuum environment of 0.05MPa, the treatment temperature is 70 ℃, and the treatment time is 30 min; the temperature of the curing treatment is 125 ℃, the treatment time is 25min, the temperature is increased to 125 ℃, and the treatment time is 25min, so that the formaldehyde purification ecological impregnated paper is obtained.
It should be noted that, unless otherwise stated, the mass fraction of the formaldehyde solution in the invention is 39%; the mass fraction of the sodium hydroxide solution is 42 percent.
The modified base resin colloid prepared in this example was milky white in appearance, had a solid content of 45%, and a viscosity of 158Pa · s at 20 ℃.
Example 2: preparation of formaldehyde purification ecological impregnated paper
First, preparation of lignin gel microporous powder
1) Preparation of lignin gel precursor solution
Adding lignin into absolute ethyl alcohol according to a solid-liquid ratio of 1:30, carrying out ultrasonic extraction at 35 ℃, and filtering to obtain a lignin extract; mixing 100 parts by weight of lignin extract and 300 parts by weight of deionized water according to the weight part ratio, stirring for 20min at the temperature of-5 ℃, adding 19 parts by weight of 0.15mol/L acetic acid solution into a reaction system, and carrying out ultrasonic treatment for 30min to obtain lignin gel precursor solution;
2) lignin wet gel preparation and purification treatment
Stirring the gel precursor solution at-2 deg.C for 180min, and standing for 12 hr to obtain lignin wet gel;
immersing the lignin wet gel into a supercritical purifier stored with absolute ethyl alcohol for purification treatment;
3) shaping process
Pre-cooling purified lignin wet gel at-15 deg.C for 3h, freezing in liquid nitrogen for 2min, pulverizing, and vacuum drying at 105 deg.C for 20min to obtain lignin gel microporous powder;
secondly, preparing lignin extracting solution
Uniformly mixing 100 parts by weight of lignin, 500 parts by weight of hydrogen peroxide with the mass fraction of 40% and 12 parts by weight of zinc chloride, reacting at the temperature of 180 ℃ for 80min, cooling to room temperature, and filtering to obtain a lignin extracting solution;
preparation of modified matrix resin colloid
1) Adding 95 parts by weight of lignin extracting solution, 20 parts by weight of first urea and 150 parts by weight of first formaldehyde solution into a reaction kettle according to the weight parts, and heating to 90 ℃ for reaction for 40 min;
2) adding 60 parts by weight of second urea, 120 parts by weight of second formaldehyde solution and 70 parts by weight of sodium hydroxide solution into a reaction system, and reacting at 85 ℃ for 60 min;
3) adding 150 parts by weight of a third batch of formaldehyde solution and 50 parts by weight of sodium hydroxide solution into the reaction system, and reacting for 60min at the temperature of 90 ℃;
4) adding 70 parts by weight of third batch of urea, 80 parts by weight of lignin gel microporous powder and 50 parts by weight of sodium hydroxide solution into a reaction system, stirring and reacting for 30min at 80 ℃, cooling and discharging to obtain modified matrix resin colloid;
fourth, dipping treatment
1) Drying and pretreating the base paper at 50 ℃;
2) soaking the dried and pretreated base paper in the modified matrix resin adhesive at the temperature of 40 ℃, wherein the soaking amount of the soaking treatment is 15g/m2-35g/m2Obtaining impregnated paper;
3) sequentially carrying out supercritical dryer treatment, pre-setting treatment and curing treatment on the impregnated paper, wherein the medium of the supercritical drying treatment is carbon dioxide, and the treatment temperature is-5 ℃; the pre-setting treatment is carried out under the vacuum environment of 0.05MPa, the treatment temperature is 70 ℃, and the treatment time is 30 min; the temperature of the curing treatment is 125 ℃, the treatment time is 25min, the temperature is increased to 125 ℃, and the treatment time is 25min, so that the formaldehyde purification ecological impregnated paper is obtained.
The modified base resin colloid prepared in this example was milky white in appearance, had a solids content of 49%, and had a viscosity of 162Pa · s at 20 ℃.
Example 3: preparation of formaldehyde purification ecological impregnated paper
First, preparation of lignin gel microporous powder
1) Preparation of lignin gel precursor solution
Adding lignin into absolute ethyl alcohol according to a solid-liquid ratio of 1:30, carrying out ultrasonic extraction at 35 ℃, and filtering to obtain a lignin extract; mixing 100 parts by weight of lignin extract and 300 parts by weight of deionized water according to the weight part ratio, stirring for 20min at the temperature of-5 ℃, adding 19 parts by weight of 0.15mol/L acetic acid solution into a reaction system, and carrying out ultrasonic treatment for 30min to obtain lignin gel precursor solution;
2) lignin wet gel preparation and purification treatment
Stirring the gel precursor solution at-2 deg.C for 180min, and standing for 12 hr to obtain lignin wet gel;
immersing the lignin wet gel into a supercritical purifier stored with absolute ethyl alcohol for purification treatment;
3) shaping process
Pre-cooling purified lignin wet gel at-15 deg.C for 3h, freezing in liquid nitrogen for 2min, pulverizing, and vacuum drying at 105 deg.C for 20min to obtain lignin gel microporous powder;
secondly, preparing lignin extracting solution
Uniformly mixing 100 parts by weight of lignin, 500 parts by weight of hydrogen peroxide with the mass fraction of 40% and 12 parts by weight of zinc chloride, reacting at the temperature of 180 ℃ for 80min, cooling to room temperature, and filtering to obtain a lignin extracting solution;
preparation of modified matrix resin colloid
1) Adding 115 parts by weight of lignin extracting solution, 20 parts by weight of first urea and 150 parts by weight of first formaldehyde solution into a reaction kettle, and heating to 90 ℃ for reaction for 40 min;
2) adding 60 parts by weight of second urea, 120 parts by weight of second formaldehyde solution and 70 parts by weight of sodium hydroxide solution into a reaction system, and reacting at 85 ℃ for 60 min;
3) adding 150 parts by weight of a third batch of formaldehyde solution and 50 parts by weight of sodium hydroxide solution into the reaction system, and reacting for 60min at the temperature of 90 ℃;
4) adding 70 parts by weight of third batch of urea, 100 parts by weight of lignin gel microporous powder and 50 parts by weight of sodium hydroxide solution into a reaction system, stirring and reacting for 30min at 80 ℃, cooling and discharging to obtain modified matrix resin colloid;
fourth, dipping treatment
1) Drying and pretreating the base paper at 50 ℃;
2) soaking the dried and pretreated base paper in the modified matrix resin adhesive at the temperature of 40 ℃, wherein the soaking amount of the soaking treatment is 15g/m2-35g/m2Obtaining impregnated paper;
3) sequentially carrying out supercritical dryer treatment, pre-setting treatment and curing treatment on the impregnated paper, wherein the medium of the supercritical drying treatment is carbon dioxide, and the treatment temperature is-5 ℃; the pre-setting treatment is carried out under the vacuum environment of 0.05MPa, the treatment temperature is 70 ℃, and the treatment time is 30 min; the temperature of the curing treatment is 125 ℃, the treatment time is 25min, the temperature is increased to 125 ℃, and the treatment time is 25min, so that the formaldehyde purification ecological impregnated paper is obtained.
The modified base resin colloid prepared in this example was milky white in appearance, had a solids content of 55%, and a viscosity of 165Pa · s at 20 ℃, and the formaldehyde-purified ecological impregnated paper prepared using the modified base resin colloid of this example did not contain free formaldehyde.
Example 4: preparation of formaldehyde purification ecological impregnated paper
First, preparation of lignin gel microporous powder
1) Preparation of lignin gel precursor solution
Adding lignin into absolute ethyl alcohol according to a solid-liquid ratio of 1:30, carrying out ultrasonic extraction at 35 ℃, and filtering to obtain a lignin extract; mixing 100 parts by weight of lignin extract and 300 parts by weight of deionized water according to the weight part ratio, stirring for 20min at the temperature of-5 ℃, adding 19 parts by weight of 0.15mol/L acetic acid solution into a reaction system, and carrying out ultrasonic treatment for 30min to obtain lignin gel precursor solution;
2) lignin wet gel preparation and purification treatment
Stirring the gel precursor solution at-2 deg.C for 180min, and standing for 12 hr to obtain lignin wet gel;
immersing the lignin wet gel into a supercritical purifier stored with absolute ethyl alcohol for purification treatment;
3) shaping process
Pre-cooling purified lignin wet gel at-15 deg.C for 3h, freezing in liquid nitrogen for 2min, pulverizing, and vacuum drying at 105 deg.C for 20min to obtain lignin gel microporous powder;
secondly, preparing lignin extracting solution
Uniformly mixing 100 parts by weight of lignin, 500 parts by weight of hydrogen peroxide with the mass fraction of 40% and 12 parts by weight of zinc chloride, reacting at the temperature of 180 ℃ for 80min, cooling to room temperature, and filtering to obtain a lignin extracting solution;
preparation of modified matrix resin colloid
1) Adding 125 parts by weight of lignin extracting solution, 20 parts by weight of first urea and 150 parts by weight of first formaldehyde solution into a reaction kettle, and heating to 90 ℃ for reaction for 40 min;
2) adding 60 parts by weight of second urea, 120 parts by weight of second formaldehyde solution and 70 parts by weight of sodium hydroxide solution into a reaction system, and reacting at 85 ℃ for 60 min;
3) adding 150 parts by weight of a third batch of formaldehyde solution and 50 parts by weight of sodium hydroxide solution into the reaction system, and reacting for 60min at the temperature of 90 ℃;
4) adding 70 parts by weight of third batch of urea, 130 parts by weight of lignin gel microporous powder and 50 parts by weight of sodium hydroxide solution into a reaction system, stirring and reacting for 30min at 80 ℃, cooling and discharging to obtain modified matrix resin colloid;
fourth, dipping treatment
1) Drying and pretreating the base paper at 50 ℃;
2) soaking the dried and pretreated base paper in the modified matrix resin adhesive at the temperature of 40 ℃, wherein the soaking amount of the soaking treatment is 15g/m2-35g/m2Obtaining impregnated paper;
3) sequentially carrying out supercritical dryer treatment, pre-setting treatment and curing treatment on the impregnated paper, wherein the medium of the supercritical drying treatment is carbon dioxide, and the treatment temperature is-5 ℃; the pre-setting treatment is carried out under the vacuum environment of 0.05MPa, the treatment temperature is 70 ℃, and the treatment time is 30 min; the temperature of the curing treatment is 125 ℃, the treatment time is 25min, the temperature is increased to 125 ℃, and the treatment time is 25min, so that the formaldehyde purification ecological impregnated paper is obtained.
The modified base resin colloid prepared in this example was milky white in appearance, had a solids content of 58%, and had a viscosity of 162Pa · s at 20 ℃.
Example 5: preparation of formaldehyde purification ecological impregnated paper
First, preparation of lignin gel microporous powder
1) Preparation of lignin gel precursor solution
Adding lignin into absolute ethyl alcohol according to a solid-liquid ratio of 1:30, carrying out ultrasonic extraction at 35 ℃, and filtering to obtain a lignin extract; mixing 100 parts by weight of lignin extract and 300 parts by weight of deionized water according to the weight part ratio, stirring for 20min at the temperature of-5 ℃, adding 19 parts by weight of 0.15mol/L acetic acid solution into a reaction system, and carrying out ultrasonic treatment for 30min to obtain lignin gel precursor solution;
2) lignin wet gel preparation and purification treatment
Stirring the gel precursor solution at-2 deg.C for 180min, and standing for 12 hr to obtain lignin wet gel;
immersing the lignin wet gel into a supercritical purifier stored with absolute ethyl alcohol for purification treatment;
3) shaping process
Pre-cooling purified lignin wet gel at-15 deg.C for 3h, freezing in liquid nitrogen for 2min, pulverizing, and vacuum drying at 105 deg.C for 20min to obtain lignin gel microporous powder;
secondly, preparing lignin extracting solution
Uniformly mixing 100 parts by weight of lignin, 500 parts by weight of hydrogen peroxide with the mass fraction of 40% and 12 parts by weight of zinc chloride, reacting at the temperature of 180 ℃ for 80min, cooling to room temperature, and filtering to obtain a lignin extracting solution;
preparation of modified matrix resin colloid
1) Adding 150 parts by weight of lignin extracting solution, 20 parts by weight of first urea and 150 parts by weight of first formaldehyde solution into a reaction kettle, and heating to 90 ℃ for reaction for 40 min;
2) adding 60 parts by weight of second urea, 120 parts by weight of second formaldehyde solution and 70 parts by weight of sodium hydroxide solution into a reaction system, and reacting at 85 ℃ for 60 min;
3) adding 150 parts by weight of a third batch of formaldehyde solution and 50 parts by weight of sodium hydroxide solution into the reaction system, and reacting for 60min at the temperature of 90 ℃;
4) adding 70 parts by weight of third batch of urea, 150 parts by weight of lignin gel microporous powder and 50 parts by weight of sodium hydroxide solution into a reaction system, stirring and reacting for 30min at 80 ℃, cooling and discharging to obtain modified matrix resin colloid;
fourth, dipping treatment
1) Drying and pretreating the base paper at 50 ℃;
2) soaking the dried and pretreated base paper in the modified matrix resin adhesive at the temperature of 40 ℃, wherein the soaking amount of the soaking treatment is 15g/m2-35g/m2Obtaining impregnated paper;
3) sequentially carrying out supercritical dryer treatment, pre-setting treatment and curing treatment on the impregnated paper, wherein the medium of the supercritical drying treatment is carbon dioxide, and the treatment temperature is-5 ℃; the pre-setting treatment is carried out under the vacuum environment of 0.05MPa, the treatment temperature is 70 ℃, and the treatment time is 30 min; the temperature of the curing treatment is 125 ℃, the treatment time is 25min, the temperature is increased to 125 ℃, and the treatment time is 25min, so that the formaldehyde purification ecological impregnated paper is obtained.
The modified base resin colloid prepared in this example was milky white in appearance, had a solids content of 58%, and had a viscosity of 159 pas at 20 ℃.
In summary, the modified matrix resin colloid prepared in the embodiment of the present invention has a solid content of not less than 45% and a viscosity of not less than 158mPa · s at 20 ℃, and the formaldehyde-purified ecological impregnated paper prepared by using the modified matrix resin colloid of the embodiment does not contain free formaldehyde.
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 utility model provides a formaldehyde purifies ecological impregnated paper, its characterized in that, formaldehyde purifies ecological impregnated paper includes body paper and the modified matrix resin colloid of dip coating in the body paper outside, modified matrix resin colloid raw materials include: 80-150 parts of lignin extract, 150 parts of urea, 420 parts of formaldehyde solution, 50-150 parts of lignin gel microporous powder and 170 parts of sodium hydroxide solution; wherein, the raw materials of the lignin extracting solution comprise: 100 parts by weight of lignin, 500 parts by weight of hydrogen peroxide and 12 parts by weight of zinc chloride; the lignin gel microporous powder comprises the following raw materials: absolute ethyl alcohol, lignin, deionized water, an acetic acid solution and liquid nitrogen; the solid content of the modified matrix resin colloid is not less than 45%, and the viscosity at 20 ℃ is not less than 158 mPas.
2. A preparation method of formaldehyde-purifying ecological impregnated paper is characterized by comprising the following steps:
first, preparation of lignin gel microporous powder
1) Preparation of lignin gel precursor solution
Adding lignin into absolute ethyl alcohol according to a solid-liquid ratio of 1:30, carrying out ultrasonic extraction at 35 ℃, and filtering to obtain a lignin extract; mixing 100 parts by weight of lignin extract and 300 parts by weight of deionized water according to the weight part ratio, stirring for 20min at the temperature of-5 ℃, adding 19 parts by weight of 0.15mol/L acetic acid solution into a reaction system, and carrying out ultrasonic treatment for 30min to obtain lignin gel precursor solution;
2) lignin wet gel preparation and purification treatment
Stirring the gel precursor solution at-2 deg.C for 180min, and standing for 12 hr to obtain lignin wet gel;
immersing the lignin wet gel into a supercritical purifier stored with absolute ethyl alcohol for purification treatment;
3) shaping process
Pre-cooling purified lignin wet gel at-15 deg.C for 3h, freezing in liquid nitrogen for 2min, pulverizing, and vacuum drying at 105 deg.C for 20min to obtain lignin gel microporous powder;
secondly, preparing lignin extracting solution
Uniformly mixing 100 parts by weight of lignin, 500 parts by weight of hydrogen peroxide with the mass fraction of 40% and 12 parts by weight of zinc chloride, reacting at the temperature of 180 ℃ for 80min, cooling to room temperature, and filtering to obtain a lignin extracting solution;
preparation of modified matrix resin colloid
1) Adding 80-150 parts by weight of lignin extracting solution, 20 parts by weight of first urea and 150 parts by weight of first formaldehyde solution into a reaction kettle according to the weight parts, and heating to 90 ℃ for reaction for 40 min;
2) adding 60 parts by weight of second urea, 120 parts by weight of second formaldehyde solution and 70 parts by weight of sodium hydroxide solution into a reaction system, and reacting at 85 ℃ for 60 min;
3) adding 150 parts by weight of a third batch of formaldehyde solution and 50 parts by weight of sodium hydroxide solution into the reaction system, and reacting for 60min at the temperature of 90 ℃;
4) adding 70 parts by weight of third batch of urea, 50-150 parts by weight of lignin gel microporous powder and 50 parts by weight of sodium hydroxide solution into a reaction system, stirring and reacting at 80 ℃ for 30min, cooling and discharging to obtain modified matrix resin colloid;
fourth, dipping treatment
1) Drying and pretreating the base paper at 50 ℃;
2) soaking the dried and pretreated base paper in the modified matrix resin adhesive at the temperature of 40 ℃ to obtain impregnated paper;
3) sequentially carrying out supercritical dryer treatment, presetting treatment and curing treatment on the impregnated paper; heating to 125 ℃, and treating for 25min to obtain the formaldehyde-purified ecological impregnated paper.
3. The production method according to claim 2, wherein the impregnation amount of the impregnation treatment is 15g/m2-35g/m2。
4. The method according to claim 2, wherein the supercritical drying medium is carbon dioxide and the treatment temperature is-5 ℃.
5. The method according to claim 2, wherein the pre-setting treatment is performed under a vacuum environment of 0.05MPa at a treatment temperature of 70 ℃ for a treatment time of 30 min.
6. The method according to claim 2, wherein the curing treatment is carried out at 125 ℃ for 25 min.
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