CN113667265B - High-flame-retardance water-based phenolic resin, preparation method thereof and method for applying high-flame-retardance water-based phenolic resin to laminated board - Google Patents

High-flame-retardance water-based phenolic resin, preparation method thereof and method for applying high-flame-retardance water-based phenolic resin to laminated board Download PDF

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CN113667265B
CN113667265B CN202110839763.5A CN202110839763A CN113667265B CN 113667265 B CN113667265 B CN 113667265B CN 202110839763 A CN202110839763 A CN 202110839763A CN 113667265 B CN113667265 B CN 113667265B
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water
phenolic resin
flame
based phenolic
laminated board
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CN113667265A (en
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杨进
鄢俊
王涛
孙乐乐
李朝晖
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South China University of Technology SCUT
Southern Marine Science and Engineering Guangdong Laboratory Zhuhai
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South China University of Technology SCUT
Southern Marine Science and Engineering Guangdong Laboratory Zhuhai
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/28—Shaping operations therefor
    • B29C70/30—Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core
    • B29C70/34—Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core and shaping or impregnating by compression, i.e. combined with compressing after the lay-up operation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/28—Shaping operations therefor
    • B29C70/54—Component parts, details or accessories; Auxiliary operations, e.g. feeding or storage of prepregs or SMC after impregnation or during ageing
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2007/00—Flat articles, e.g. films or sheets
    • B29L2007/002—Panels; Plates; Sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
    • C08J2361/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08J2361/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C08J2361/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols with monohydric phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2497/00—Characterised by the use of lignin-containing materials
    • C08J2497/02—Lignocellulosic material, e.g. wood, straw or bagasse
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2217—Oxides; Hydroxides of metals of magnesium
    • C08K2003/2224—Magnesium hydroxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/321—Phosphates
    • C08K2003/322—Ammonium phosphate
    • C08K2003/323—Ammonium polyphosphate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/04—Polymer mixtures characterised by other features containing interpenetrating networks

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
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  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Phenolic Resins Or Amino Resins (AREA)
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  • Laminated Bodies (AREA)

Abstract

The invention discloses a high-flame-retardance water-based phenolic resin, a preparation method thereof and a method for applying the high-flame-retardance water-based phenolic resin to a laminated board. In the method, the position and the content of hydroxymethyl groups are controlled to prepare the water-borne phenolic resin. And then, utilizing hydrosilylation reaction to successfully graft polyoxyethylene ether and the side chain of glycidyl ether on the molecular chain of the silicone oil. The water-based phenolic resin is prepared by compounding with the water-based phenolic resin, and due to the introduction of an epoxy group, the organic silicon and the phenolic resin are combined through chemical bonds to form a compact cross-linked structure with an interpenetrating network structure, so that the water resistance of the resin is improved, and meanwhile, the high temperature resistance and the heat resistance of the resin can be improved by the organic siloxane. The water-based phenolic resin prepared by the method meets the preparation requirement of environmental protection, and the laminated board prepared by the method has better mechanical property, flame retardant property, water resistance, corrosion resistance, processability and service performance, and can meet the application requirements of various buildings and furniture.

Description

High-flame-retardance water-based phenolic resin, preparation method thereof and method for applying high-flame-retardance water-based phenolic resin to laminated board
Technical Field
The invention belongs to the field of laminated boards, and particularly relates to a high-flame-retardant water-based phenolic resin and a preparation method of a laminated board.
Background
In recent years, with the rapid development of social economy, the scope of construction projects in China is continuously expanded, and the demand of building materials is continuously increased along with the rise of the construction industry. The wood building materials have wide raw materials, simple and convenient manufacture and lower cost, and have a certain share in the building material market, but most of the wood building materials are made of plant fiber materials, and due to the moisture absorption effect, the performance can be greatly reduced after long-time use, the service life can be shortened, and certain potential safety hazards can be caused. The laminated board prepared with phenolic resin may be used widely as beam, column, wall, unidirectional board and other structural members in building structure owing to its large size range, high mechanical performance, water resistance and corrosion resistance. Meanwhile, the national places more and more attention on the safety performance of materials and also puts higher demands on the flame retardance of building materials.
Phenolic resin has been one of three synthetic thermosetting resins, has been used for nearly one hundred years and is widely used as molding compounds, adhesives, coatings, foamed plastics, printing ink and the like, and meanwhile, the phenolic resin has good insulativity, heat resistance, flame retardance and corrosion resistance and is applied to various fields of national defense, military industry, buildings, traffic, aerospace, ships and the like. However, because of inherent brittleness, insufficient toughness and poor impact resistance, the development of the phenolic resin is limited, and meanwhile, the preparation of the phenolic resin usually uses alcohol as a solvent, so that the problems of environmental pollution, harm to the health and safety of operators and the like are solved, so that in the actual use of the phenolic resin, some modification means are usually required to overcome the defects, and meanwhile, an aqueous medium is required to be used as the solvent in the production process, so that the safety of the operators is guaranteed.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of high-flame-retardant water-based phenolic aldehyde and a laminated board, on one hand, the water-based phenolic aldehyde resin is prepared by controlling the position and the content of a hydroxymethyl group, the problems of environmental pollution, safety and the like caused by solvent volatilization in the preparation can be solved, and simultaneously the water-based phenolic aldehyde resin is modified, and the water-dispersible flexible polyether and the reactive glycidyl ether are introduced to serve as an organic siloxane structure of a side chain, so that the organic siloxane structure is toughened, the inherent brittleness is improved, a compact cross-linked structure with an interpenetrating network structure is formed, the water resistance is improved, and meanwhile, the high-temperature resistance and the damp-heat resistance of the resin can be improved; on the other hand, the flame retardant is added into the compound resin in a mechanical mixing mode, so that the flame retardant property of the resin can be greatly improved; finally, the high-flame-retardant water-based phenolic resin is used as an impregnation system of the laminated board, and the prepared laminated board has good mechanical property, flame retardant property, water resistance, corrosion resistance, processability and service performance, and can meet the application requirements of various buildings and furniture.
The technical scheme of the invention is as follows:
a preparation method of high flame retardant water-based phenolic resin comprises the following steps:
s1, adding 15-25 parts of phenolic substances, 2-5 parts of sodium hydroxide, 15-25 parts of deionized water and 20-30 parts of formaldehyde into a reaction container, heating to 55-65 ℃, and reacting for 1-2 hours under the condition of heat preservation;
s2, continuously heating to 75-85 ℃ in the reaction container in the step S1, adding 10-15 parts of second batch of formaldehyde according to the formula, and continuously reacting for 0.5-1h under the condition of heat preservation;
s3, adding 5-8 parts of alkylphenol and 10-20 parts of deionized water into the reaction container in the step S2, and continuously reacting for 0.5-1h at the temperature of 75-85 ℃ to obtain water-based phenolic resin;
s4, adding 60-65 parts of allyl polyether substance, 20-25 parts of water carrying agent and 0.1-0.3 part of catalyst into a reaction container, heating to 60-70 ℃, and reacting for 0.5-1h under the condition of heat preservation;
s5, in the reaction container of the step S4, heating to the temperature of 130-;
s6, cooling to 80-90 ℃ in the reaction container in the step S5, adding 3-4 parts of allyl glycidyl ether, and reacting for 2-4 hours under the condition of heat preservation;
s7, pouring the solution obtained in the step S6 into a flask, and removing the solvent by using a rotary evaporator to obtain a modifier of the phenolic resin, namely side chain organic silicone oil;
s8, mixing the water-based phenolic resin obtained in the step S3 with the side chain organic silicone oil obtained in the step S7, wherein the addition amount of the side chain organic silicone oil satisfies the following conditions: the side chain organic silicone oil accounts for 3-5 percent of the total mass, and the side chain organic silicone oil is put into a water bath kettle, the temperature is controlled at 45-55 ℃, the stirring speed is 1000-2000r/min, and the compound resin is obtained.
S9, adding 3-5% of flame retardant into the compound resin obtained in the step S8, and uniformly mixing under a stirring state to obtain high-flame-retardant water-based phenolic resin; the flame retardant comprises: ammonium polyphosphate, phosphorus pentoxide, expanded graphite, silicon dioxide, melamine, aluminum hydroxide, magnesium hydroxide, boric acid and borate.
Preferably, in step S1, the phenolic substance includes a mixture of phenol and other phenols, the other phenols are selected from more than one of xylenol, cresol, m-cresol, resorcinol, bisphenol a or bisphenol F, and the added mass is calculated by mass percentage, wherein the phenol accounts for 80% -100% of the total mass of the phenolic substance.
Preferably, the charging sequence for step S1 is: phenolic substances, formaldehyde, deionized water and sodium hydroxide.
Preferably, in S3, the alkylphenol is selected from one or more of methylphenol, m-methylphenol, dimethylphenol, ethylphenol, propylphenol, butylphenol, pentylphenol, heptylphenol, octylphenol, nonylphenol, and decylphenol.
Preferably, in S5, the hydrogen-containing silicone oil may include one of a silicone oil with a hydrogen content of 0.25, a silicone oil with a hydrogen content of 0.5, a silicone oil with a hydrogen content of 1.0, and a silicone oil with a hydrogen content of 1.5.
Preferably, in step S4, the polyether substance includes one or more of allyl polyoxyethylene ether, allyl polyoxypropylene ether, allyl polyoxyethylene oxypropylene ether, polyoxyethylene fatty alcohol ether, and diallyl polyether.
Preferably, in step S4, the polyether is allyl polyoxyethylene ether.
Preferably, in step S4, the water carrying agent includes one or more of toluene, xylene, cyclohexane, chloroform, and carbon tetrachloride.
Preferably, in step S4, the water carrying agent is toluene.
Preferably, in step S4, the catalyst includes one or more of chloroplatinic acid, rhodium, ruthenium, iron, and cobalt, preferably chloroplatinic acid.
The method for applying the high-flame-retardancy water-based phenolic resin to the laminated board comprises the following steps of:
A1. naturally weathering and drying the plant fiber material, controlling the water content to be 4% -8%, carrying out cold pressing treatment, and preparing the plant fiber material into a sheet shape, wherein the plant fiber material needs to be cut for subsequent convenient preparation, and meanwhile, the plant fiber material needs to be further cold pressed for better immersing resin until the plant fiber material is crushed; the plant fiber material comprises: one of wood, nettle, ramie, rice straw, bamboo, cotton stalk and wheat stalk;
A2. putting the flaky plant fiber material prepared in the step A1 into an impregnation container, adding high-flame-retardant water-based phenolic resin, controlling the phenolic resin to completely immerse the material, and impregnating for 1h in the state;
A3. taking out the flaky plant fiber material obtained in the step A2, treating redundant resin on the surface, putting the treated flaky plant fiber material into an oven, and drying the flaky plant fiber material at the temperature of 80 ℃ until the water content reaches 12-15%;
A4. taking out the prepreg obtained in the step A3, cooling, stacking into a mold, performing hot pressing treatment, and controlling the pressure per unit area to be 6-8N/mm 2 Controlling the heating temperature to be 140-150 ℃, controlling the central temperature of the processed material to be 140 ℃, carrying out hot pressing for 0.5h, then stopping heating, immediately cooling, unloading the laminated board when the central temperature of the laminated board is lower than 60 ℃, and controlling the gluing amount of the laminated board to be 20%;
A5. and D, placing the laminated board obtained in the step A4 at normal temperature for 1h, cooling, and trimming to obtain the high-flame-retardancy water-based phenolic resin laminated board.
The invention provides a high-flame-retardant water-based phenolic resin laminated board prepared by the method.
Compared with the prior art, the invention has the following advantages:
1. at present, most of phenolic resins mostly adopt alcohol as a solvent in the preparation process, so that the environment is polluted, the body of an operator is damaged, and certain potential safety hazards exist. The water-based resin prepared by the invention takes water as a solvent, so that the problem of environmental pollution is greatly reduced, the environment-friendly preparation requirement is met, the safety coefficient is improved, and the physical health of operators is guaranteed; meanwhile, through hydrosilylation reaction, polyoxyethylene ether and side chains of glycidyl ether are successfully grafted on a molecular chain of silicone oil, and the water-based phenolic resin is compounded with the water-based phenolic resin to prepare the water-based phenolic resin with polyether and organic siloxane for synergistic toughening modification, so that the inherent brittleness of the water-based phenolic resin is greatly improved, the water dispersibility is provided by introducing the polyether, the water resistance is improved by introducing the reactive condensed ether, the cross-linking structure of the resin is improved, and the high temperature resistance and the damp-heat resistance of the resin can be improved by the siloxane; in addition, the flame retardant is added into the compound resin in a mechanical mixing mode, so that the flame retardant property of the phenolic resin is further improved.
2. The invention is applied to the preparation of the laminated board, and the prepared laminated board has better mechanical property, flame retardant property, water resistance, corrosion resistance, processing property and service performance, and meets the application requirements of various buildings and furniture;
3. the method has the advantages of simple process, simple and convenient operation and low cost of each raw material, and is suitable for large-scale industrial production.
Detailed Description
The present invention is described in detail below by way of examples, it being necessary here to point out that the examples are given for the purpose of further illustration only and are not to be construed as limiting the scope of the invention, which is to be construed as numerous insubstantial modifications and adaptations by those skilled in the art in view of the present invention.
Firstly, the position and the content of hydroxymethyl groups are controlled to prepare the water-borne phenolic resin. And then, by utilizing hydrosilylation reaction, the side chains of polyoxyethylene ether and glycidyl ether are successfully grafted on the molecular chain of the silicone oil, so that the organic silicone oil is endowed with dispersibility in water. The polyether and organic siloxane synergistic toughening modified aqueous phenolic resin is prepared by further compounding with the aqueous phenolic resin, the inherent brittleness of the aqueous phenolic resin is greatly improved, organic silicon and the phenolic resin are combined through chemical bonds due to the introduction of an epoxy group to form a compact cross-linked structure with an interpenetrating network structure, the water resistance of the aqueous phenolic resin is improved, and meanwhile, the organic siloxane can also improve the high temperature resistance and the moisture resistance of the resin. In addition, the flame retardant is added into the compound resin in a mechanical mixing mode, so that the flame retardant property of the compound resin is improved. Finally, the composite material is applied to the preparation of the laminated board. The water-based phenolic resin prepared by the method meets the preparation requirement of environmental protection, and on the other hand, the water-based phenolic resin is compounded with side chain organic silicone oil and a flame retardant to be applied to the preparation of the laminated board.
Example 1
The embodiment provides a preparation method of a high-flame-retardance water-borne phenolic resin and a laminated board, which comprises the following steps: preparing high-flame-retardant water-based phenolic resin:
(1) sequentially adding 10g of phenol, 13g of formaldehyde, 10g of deionized water and 1.25g of sodium hydroxide into a reaction container according to the charging sequence, heating to 60 ℃, and reacting for 2 hours under the heat preservation condition; continuously heating to 80 ℃, adding 6g of second batch of formaldehyde according to the formula, and continuously reacting for 0.5h under the condition of heat preservation; adding 3.25g of m-methyl phenol and 8g of deionized water, and continuously reacting for 0.5h at the temperature of 80 ℃ to obtain water-based phenolic resin;
(2) adding 20.25g of allyl polyoxyethylene ether, 7.28g of toluene and 0.07g of chloroplatinic acid into a reaction vessel, heating to 65 ℃, and reacting for 0.5h under the condition of heat preservation; raising the temperature to 135 ℃, adding 3g of silicone oil with the hydrogen content of 1.0, and reacting for 3 hours under the condition of heat preservation; reducing the temperature to 85 ℃, adding 1.027g of allyl glycidyl ether, and reacting for 3h under the condition of heat preservation; pouring the obtained solution into a flask, and removing the solvent by using a rotary evaporator to obtain side chain organic silicone oil;
(3) and (3) mixing the water-based phenolic resin obtained in the step (1) with the side chain organic silicone oil obtained in the step (2), placing the mixture into a water bath kettle, controlling the temperature at 50 ℃ and the stirring speed at 1000-2000r/min to obtain the compound resin.
(4) Mixing the compound resin obtained in the step (3) with ammonium polyphosphate under a stirring state to obtain the high-flame-retardancy water-based phenolic resin, wherein the addition amount of the ammonium polyphosphate is 3%;
preparation of the laminate:
naturally weathering and drying the cotton straws, controlling the water content to be 4% -8%, carrying out cold pressing treatment, and making the cotton straws into sheets, wherein the cotton straws need to be cut for subsequent convenient preparation, and meanwhile, the cotton straws need to be further cold pressed until the cotton straws are crushed for better resin to permeate into the straws; putting the flaky cotton straws into an impregnation container, adding the prepared organic silicon modified water-based phenolic resin, controlling the phenolic resin to completely immerse the cotton straws, and impregnating for 1h in the state; taking out the cotton straws after impregnation, treating redundant resin on the surface, putting the treated cotton straws into an oven, and drying at the temperature of 80 ℃ until the water content reaches 12-15%; then taking out, cooling, stacking in a mold, performing hot pressing treatment, and controlling the pressure per unit area to be 7N/mm 2 Controlling the temperature at 150 ℃, controlling the central temperature of the processed material at 140 ℃, hot-pressing for 0.5h, then stopping heating, immediately cooling, unloading the laminated board when the central temperature of the material is lower than 60 ℃, and controlling the gluing amount of the laminated board to be 20%; and (3) placing the obtained laminated board for 1h at normal temperature, cooling, and cutting burrs to finish the preparation of the high-flame-retardancy water-based phenolic resin laminated board.
Example 2
The embodiment provides a preparation method of a high-flame-retardance water-borne phenolic resin and a laminated board, which comprises the following steps:
preparing high-flame-retardant water-based phenolic resin:
(1) sequentially adding 10g of m-cresol, 13g of formaldehyde, 10g of deionized water and 1.25g of sodium hydroxide into a reaction vessel according to the charging sequence, heating to 60 ℃, and reacting for 2 hours under the heat preservation condition; continuously heating to 80 ℃, adding 6g of second batch of formaldehyde according to the formula, and continuously reacting for 0.5h under the condition of heat preservation; adding 3.25g of m-methyl phenol and 8g of deionized water, and continuously reacting for 0.5h at the temperature of 80 ℃ to obtain water-based phenolic resin;
(2) adding 20.25g of allyl polyoxypropylene ether, 7.28g of toluene and 0.07g of chloroplatinic acid into a reaction vessel, heating to 65 ℃, and reacting for 0.5h under the condition of heat preservation; raising the temperature to 135 ℃, adding 3g of silicone oil with the hydrogen content of 1.0, and reacting for 3 hours under the condition of heat preservation; reducing the temperature to 85 ℃, adding 1.027g of allyl glycidyl ether, and reacting for 3h under the condition of heat preservation; pouring the obtained solution into a flask, and removing the solvent by using a rotary evaporator to obtain side chain organic silicone oil;
(3) and (3) mixing the water-based phenolic resin obtained in the step (1) with the side chain organic silicone oil obtained in the step (2), placing the mixture into a water bath kettle, controlling the temperature at 50 ℃ and the stirring speed at 1000-2000r/min to obtain the compound resin.
(4) Mixing the compound resin obtained in the step (3) with melamine under a stirring state to obtain high-flame-retardancy water-based phenolic resin, wherein the addition amount of the melamine is 3%;
the method for preparing the high flame retardant water-based phenolic resin laminated board of the embodiment is the same as the embodiment 1.
Example 3
The embodiment provides a preparation method of a high-flame-retardance water-borne phenolic resin and a laminated board, which comprises the following steps:
preparing high-flame-retardant water-based phenolic resin:
(1) sequentially adding 10g of phenol, 13g of formaldehyde, 10g of deionized water and 1.25g of sodium hydroxide into a reaction container according to the charging sequence, heating to 60 ℃, and reacting for 2 hours under the heat preservation condition; continuously heating to 80 ℃, adding 6g of second batch of formaldehyde according to the formula, and continuously reacting for 0.5h under the condition of heat preservation; adding 3.25g of dimethyl phenol and 8g of deionized water, and continuously reacting for 0.5h at the temperature of 80 ℃ to obtain water-based phenolic resin;
(2) adding 20.25g of allyl polyoxyethylene ether, 7.28g of toluene and 0.07g of chloroplatinic acid into a reaction vessel, heating to 65 ℃, and reacting for 0.5h under the condition of heat preservation; raising the temperature to 135 ℃, adding 3g of silicone oil with the hydrogen content of 1.5, and reacting for 3 hours under the condition of heat preservation; reducing the temperature to 85 ℃, adding 1.027g of allyl glycidyl ether, and reacting for 3h under the condition of heat preservation; pouring the obtained solution into a flask, and removing the solvent by using a rotary evaporator to obtain side chain organic silicone oil;
(3) and (3) mixing the water-based phenolic resin obtained in the step (1) with the side chain organic silicone oil obtained in the step (2), wherein the addition amount of the side chain organic silicone oil is 5%, placing the mixture into a water bath kettle, controlling the temperature at 50 ℃ and the stirring speed at 1000-2000r/min, and obtaining the compound resin.
(4) Mixing the compound resin obtained in the step (3) with magnesium hydroxide under a stirring state to obtain the high-flame-retardancy water-based phenolic resin, wherein the addition amount of the magnesium hydroxide is 3%;
the method for preparing the high flame retardant water phenolic resin laminated board of the embodiment is the same as the embodiment 1.
Example 4
The embodiment provides a preparation method of a high-flame-retardance water-borne phenolic resin and a laminated board, which comprises the following steps:
preparing high-flame-retardant water-based phenolic resin:
(1) sequentially adding 10g of phenol, 13g of formaldehyde, 10g of deionized water and 1.25g of sodium hydroxide into a reaction container according to the charging sequence, heating to 60 ℃, and reacting for 2 hours under the heat preservation condition; continuously heating to 80 ℃, adding 6g of second batch of formaldehyde according to the formula, and continuously reacting for 0.5h under the condition of heat preservation; adding 3.25g of ethyl phenol and 8g of deionized water, and continuously reacting for 0.5h at the temperature of 80 ℃ to obtain water-based phenolic resin;
(2) adding 20.25g of allyl polyoxyethylene oxypropylene ether, 7.28g of toluene and 0.07g of chloroplatinic acid into a reaction vessel, heating to 65 ℃, and reacting for 0.5h under the condition of heat preservation; raising the temperature to 135 ℃, adding 3g of silicone oil with the hydrogen content of 1.0, and reacting for 3 hours under the condition of heat preservation; reducing the temperature to 85 ℃, adding 1.027g of allyl glycidyl ether, and reacting for 3h under the condition of heat preservation; pouring the obtained solution into a flask, and removing the solvent by using a rotary evaporator to obtain side chain organic silicone oil;
(3) and (3) mixing the water-based phenolic resin obtained in the step (1) with the side chain organic silicone oil obtained in the step (2), wherein the addition amount of the side chain organic silicone oil is 4%, placing the mixture into a water bath kettle, controlling the temperature at 50 ℃ and the stirring speed at 1000-2000r/min, and obtaining the compound resin.
(4) Mixing the compound resin obtained in the step (3) with boric acid under a stirring state to obtain the high-flame-retardancy water-based phenolic resin, wherein the addition amount of the boric acid is 3%;
the method for preparing the high flame retardant water-based phenolic resin laminated board of the embodiment is the same as the embodiment 1.
Comparative example 1
The comparative example provides a preparation method of high-flame-retardant water-based phenolic resin and a laminated board, and the preparation method comprises the following steps:
preparation of the aqueous phenolic resin:
(1) sequentially adding 10g of phenol, 13g of formaldehyde, 10g of deionized water and 1.25g of sodium hydroxide into a reaction container according to the charging sequence, heating to 60 ℃, and reacting for 2 hours under the heat preservation condition; continuously heating to 80 ℃, adding 6g of second batch of formaldehyde according to the formula, and continuously reacting for 0.5h under the condition of heat preservation; adding 3.25g of m-methyl phenol and 8g of deionized water, and continuously reacting for 0.5h at the temperature of 80 ℃ to obtain the water-based phenolic resin without adding side chain organic silicone oil;
(2) mixing the aqueous phenolic resin obtained in the step (1) with magnesium hydroxide under a stirring state to obtain high-flame-retardancy aqueous phenolic resin, wherein the addition amount of the magnesium hydroxide is 3%;
the method for preparing the high flame-retardant water-based phenolic resin laminated plate of the comparative example is the same as that of the example 1.
Comparative example 2
The comparative example provides a method for preparing a water-borne phenolic resin and a laminate, comprising the following steps:
preparation of the aqueous phenolic resin:
(1) sequentially adding 10g of phenol, 13g of formaldehyde, 10g of deionized water and 1.25g of sodium hydroxide into a reaction container according to the charging sequence, heating to 60 ℃, and reacting for 2 hours under the heat preservation condition; continuously heating to 80 ℃, adding 6g of second batch of formaldehyde according to the formula, and continuously reacting for 0.5h under the condition of heat preservation; adding 3.25g of m-methyl phenol and 8g of deionized water, and continuously reacting for 0.5h at the temperature of 80 ℃ to obtain water-based phenolic resin;
(2) adding 20.25g of allyl polyoxyethylene ether, 7.28g of toluene and 0.07g of chloroplatinic acid into a reaction vessel, heating to 65 ℃, and reacting for 0.5h under the condition of heat preservation; raising the temperature to 135 ℃, adding 3g of silicone oil with the hydrogen content of 1.5, and reacting for 3 hours under the condition of heat preservation; reducing the temperature to 85 ℃, adding 1.027g of allyl glycidyl ether, and reacting for 3h under the condition of heat preservation; pouring the obtained solution into a flask, and removing the solvent by using a rotary evaporator to obtain side chain organic silicone oil;
(3) mixing the water-based phenolic resin obtained in the step (1) with the side chain organic silicone oil obtained in the step (2), wherein the addition amount of the side chain organic silicone oil is 3%, placing the mixture into a water bath kettle, controlling the temperature at 50 ℃ and the stirring speed at 1000-2000r/min to obtain a compound resin, and adding no flame retardant;
the high flame retardant aqueous phenolic resin laminate of this comparative example was prepared in the same manner as in example 1.
The basic performance tests of the laminates prepared in the above examples and comparative examples are shown in the following table:
Figure BDA0003178422030000131
the present invention has been described in detail in order to enable those skilled in the art to understand the invention and to practice it, and it is not intended to limit the scope of the invention, and all equivalent changes and modifications made according to the spirit of the present invention should be covered by the present invention.

Claims (10)

1. The preparation method of the high-flame-retardance water-based phenolic resin is characterized by comprising the following steps of:
s1, adding 15-25 parts of phenolic substances, 2-5 parts of sodium hydroxide, 15-25 parts of deionized water and 20-30 parts of formaldehyde into a reaction vessel, heating to 55-65 ℃, and reacting for 1-2 hours under a heat preservation condition;
s2, continuously heating to 75-85 ℃ in the reaction container in the step S1, adding 10-15 parts of second batch of formaldehyde according to the formula, and continuously reacting for 0.5-1h under the condition of heat preservation;
s3, adding 5-8 parts of alkylphenol and 10-20 parts of deionized water into the reaction container in the step S2, and continuously reacting for 0.5-1h at the temperature of 75-85 ℃ to obtain water-based phenolic resin;
s4, adding 60-65 parts of allyl polyether substance, 20-25 parts of water carrying agent and 0.1-0.3 part of catalyst into a reaction container, heating to 60-70 ℃, and reacting for 0.5-1h under the condition of heat preservation;
s5, heating to 130-140 ℃ in the reaction container in the step S4, adding 8-10 parts of hydrogen-containing silicone oil, and reacting for 2-4h under the condition of heat preservation;
s6, cooling to 80-90 ℃ in the reaction container in the step S5, adding 3-4 parts of allyl glycidyl ether, and reacting for 2-4 hours under the condition of heat preservation;
s7, pouring the solution obtained in the step S6 into a flask, and removing the solvent by using a rotary evaporator to obtain a side chain organic silicone oil which is a modifier of the phenolic resin;
s8, mixing the water-based phenolic resin obtained in the step S3 with the side chain organic silicone oil obtained in the step S7, wherein the addition amount of the side chain organic silicone oil satisfies the following conditions: the side chain organic silicone oil accounts for 3-5% of the total mass, and is put into a water bath kettle, the temperature is controlled at 45-55 ℃, the stirring speed is 2000r/min, and the compound resin is obtained;
s9, adding 3-5% of flame retardant into the compound resin obtained in the step S8, and uniformly mixing under a stirring state to obtain high-flame-retardant water-based phenolic resin; the flame retardant comprises: ammonium polyphosphate, phosphorus pentoxide, expanded graphite, silicon dioxide, melamine, aluminum hydroxide, magnesium hydroxide, boric acid and borate.
2. The method of claim 1, wherein in step S1, the phenolic substance comprises a mixture of phenol and other phenols, the other phenols are selected from one or more of xylenol, cresol, m-cresol, resorcinol, bisphenol a, and bisphenol F, and the added phenol accounts for 80-100% of the total mass of the phenolic substance.
3. The method for preparing the high-flame-retardancy water-borne phenolic resin according to claim 1, wherein in step S4, the polyether substance comprises at least one of allyl polyoxyethylene ether, allyl polyoxypropylene ether, allyl polyoxyethylene oxypropylene ether and diallyl polyether.
4. The method for preparing the high flame-retardant water-borne phenolic resin according to claim 1, wherein in step S4, the polyether substance is allyl polyoxyethylene ether.
5. The method of claim 1, wherein in step S4, the water carrying agent comprises one or more of toluene, xylene, cyclohexane, chloroform, and carbon tetrachloride.
6. The method for preparing the high flame-retardant water-borne phenolic resin according to claim 1, wherein in step S4, the water carrying agent is toluene.
7. The method for preparing the high flame-retardant water-based phenolic resin according to claim 1, wherein in step S4, the catalyst comprises one or more of chloroplatinic acid, rhodium, ruthenium, iron, and cobalt.
8. The method for preparing the high flame-retardant water-based phenolic resin according to claim 1, wherein in step S4, the catalyst is chloroplatinic acid.
9. A high flame retardant water-borne phenolic resin prepared by the preparation method of any one of claims 1 to 8.
10. The method for applying the high flame retardant aqueous phenolic resin to the laminated board according to claim 9, is characterized by comprising the following steps:
A1. naturally weathering and drying the plant fiber material, controlling the water content to be 4% -8%, carrying out cold pressing treatment, and preparing the plant fiber material into a sheet shape, wherein the plant fiber material needs to be cut for subsequent convenient preparation, and meanwhile, the plant fiber material needs to be further cold pressed for better immersing resin until the plant fiber material is crushed; the plant fiber material comprises: one of wood, nettle, ramie, rice straw, bamboo, cotton stalk and wheat stalk;
A2. putting the flaky plant fiber material prepared in the step A1 into an impregnation container, adding high-flame-retardant water-based phenolic resin, controlling the phenolic resin to completely immerse the material, and impregnating for 1h in the state;
A3. taking out the flaky plant fiber material obtained in the step A2, treating redundant resin on the surface, putting the treated flaky plant fiber material into an oven, and drying the flaky plant fiber material at the temperature of 80 ℃ until the water content reaches 12-15%;
A4. taking out the prepreg obtained in the step A3, cooling, stacking into a mold, performing hot pressing treatment, and controlling the pressure per unit area to be 6-8N/mm 2 Controlling the heating temperature to be 140-150 ℃, controlling the central temperature of the processed material to be 140 ℃, carrying out hot pressing for 0.5h, then stopping heating, immediately cooling, unloading the laminated board when the central temperature of the laminated board is lower than 60 ℃, and controlling the gluing amount of the laminated board to be 20%;
A5. and D, placing the laminated board obtained in the step A4 at normal temperature for 1h, cooling, and trimming to obtain the high-flame-retardancy water-based phenolic resin laminated board.
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