CN111349204A - Preparation method of modified phenolic resin and foam and prepared product - Google Patents

Preparation method of modified phenolic resin and foam and prepared product Download PDF

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Publication number
CN111349204A
CN111349204A CN202010296010.XA CN202010296010A CN111349204A CN 111349204 A CN111349204 A CN 111349204A CN 202010296010 A CN202010296010 A CN 202010296010A CN 111349204 A CN111349204 A CN 111349204A
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phenolic resin
modified phenolic
foam
phenol
preparation
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吴铛
朱佳平
刘承辉
陈家荣
梁俊贤
杨晓琳
吕智杰
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Guangdong University of Petrochemical Technology
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Guangdong University of Petrochemical Technology
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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
    • 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
    • C08G12/40—Chemically modified polycondensates
    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/141—Hydrocarbons
    • 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
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • 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
    • C08J2361/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08J2361/32—Modified amine-aldehyde condensateS

Abstract

The invention discloses a modified phenolic resin, a preparation method of foam and a prepared product, wherein the phenolic resin is modified to increase a flexible chain segment and a flame-retardant element in a molecular structure, so that the toughness and the flame retardant property of a phenolic foam material are improved, the appearance and the closed porosity of cells are improved, the slag falling phenomenon of the foam material is reduced, and the modified phenolic resin is suitable for being widely popularized.

Description

Preparation method of modified phenolic resin and foam and prepared product
Technical Field
The invention relates to the technical field of phenolic resin materials, in particular to a preparation method of modified phenolic resin and foam and a prepared product.
Background
The phenolic foam is a heat-insulating material obtained by foaming phenolic resin as a main raw material, can be cast and foamed on site, can be molded and also can be machined, can be made into plates, pipe shells and various special-shaped products, has rich raw material sources, low price, simple production and processing and wide product application, and is suitable for large-scale cold storages, storage tanks, ships, various heat-insulating pipelines and building industries.
In order to improve the flame retardant property of the phenolic foam material and meet the use requirement with stricter fireproof requirements, additives such as a flame retardant and a smoke suppressant are often required to be added, but the mechanical property of the phenolic foam material is reduced, the phenolic foam is high in brittleness and easy to pulverize, the slag falling rate in the processing process is high, and potential safety hazards exist.
Disclosure of Invention
In order to solve the above problems, a first aspect of the present invention provides a method for preparing a modified phenolic resin, comprising the steps of:
a. the mixing molar ratio is 1: (1-2) adjusting the pH value of phenol and formaldehyde to 8-10 at 40-45 ℃, heating to 75-90 ℃, preserving heat for 0.5-1.5 h, and cooling to be less than or equal to 60 ℃;
b. adding melamine, heating to 65-85 ℃, and keeping the temperature for 0.5-1.5 h;
c. adding butyronitrile latex, heating to 80-105 ℃, and keeping the temperature for 0.2-0.8 h;
d. cooling to below 70 deg.C, adjusting pH to 7, and dehydrating.
As a preferable technical scheme, a NaOH solution with the weight percentage of 10-30% is used for adjusting the pH in the step a.
As a preferable technical scheme, the dosage of the melamine is 5-20 wt% of the phenol.
As a preferred technical scheme, the dosage of the butyronitrile latex is 1-30 wt% of phenol.
As a preferred technical scheme, hydrochloric acid is used for adjusting the pH in the step d.
The second aspect of the present invention provides a modified phenolic resin prepared using the preparation method as described above.
The third aspect of the invention provides a preparation method of modified phenolic foam, which comprises the following steps: and adding the surfactant, the foaming agent and the curing agent into the modified phenolic resin, stirring, pouring into a mould, and curing to obtain the modified phenolic resin.
As a preferable technical scheme, the dosage of the surfactant is 1-20 wt% of the modified phenolic resin.
As a preferable technical scheme, the amount of the foaming agent is 1-20 wt% of the modified phenolic resin.
In a fourth aspect, the present invention provides a modified phenolic foam prepared using the preparation method as described above.
Has the advantages that: the invention provides a preparation method of modified phenolic resin and foam and a prepared product, wherein the phenolic resin is modified to increase a flexible chain segment and a flame-retardant element in a molecular structure, so that the toughness and the flame retardant property of a phenolic foam material are improved, the appearance and the closed porosity of cells are improved, the slag falling phenomenon of the foam material is reduced, and the preparation method is suitable for vigorous popularization.
Drawings
To further illustrate the benefits of a method of making a modified phenolic resin and foam and the products made thereby, the accompanying drawings are provided, and it is noted that the drawings provided herein are merely selected examples of individual drawings and are not intended to be limiting of the claims, and that all other corresponding figures obtained from the drawings provided herein are to be considered within the scope of the present application.
FIG. 1 shows the reaction equation for methylol phenol and melamine.
FIG. 2 shows modified phenolic resins and modified phenolic foams obtained in examples 1 to 5 of the present invention.
FIG. 3 is an oxygen index meter used in the present invention;
reference numerals: 1-nitrogen flow regulating valve, 2-oxygen flow regulating valve, 3-sample support, 4-sample bar, 5-ignition device and 6-oxygen index numerical value display.
FIG. 4 is a graph showing comparison of oxygen indexes in examples 1 to 5 of the present invention and comparative examples 1 to 5.
FIG. 5 is a graph showing the comparison of impact strengths of examples 1 to 5 of the present invention and comparative example 1.
FIG. 6 is a scanning electron microscope image of examples 1 to 5 of the present invention and comparative example 1 at a magnification of 100, wherein a, b, c, d, e, f represent example 1, example 2, example 3, example 4, example 5, comparative example 1, respectively.
FIG. 7 is a scanning electron microscope image at 500 times for examples 1 to 5 of the present invention and comparative example 1, in which a, b, c, d, e, f represent example 1, example 2, example 3, example 4, example 5, comparative example 1, respectively.
Detailed Description
The invention will be further understood by reference to the following detailed description of preferred embodiments of the invention and the examples included therein. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. To the extent that a definition of a particular term disclosed in the prior art is inconsistent with any definitions provided herein, the definition of the term provided herein controls.
As used herein, a feature that does not define a singular or plural form is also intended to include a plural form of the feature unless the context clearly indicates otherwise. It will be further understood that the term "prepared from …," as used herein, is synonymous with "comprising," including, "comprising," "having," "including," and/or "containing," when used in this specification means that the recited composition, step, method, article, or device is present, but does not preclude the presence or addition of one or more other compositions, steps, methods, articles, or devices. Furthermore, the use of "preferred," "preferably," "more preferred," etc., when describing embodiments of the present application, is meant to refer to embodiments of the invention that may provide certain benefits, under certain circumstances. However, other embodiments may be preferred, under the same or other circumstances. In addition, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the invention.
In order to solve the above problems, a first aspect of the present invention provides a method for preparing a modified phenolic resin, comprising the steps of:
a. the mixing molar ratio is 1: (1-2) adjusting the pH value of phenol and formaldehyde to 8-10 at 40-45 ℃, heating to 75-90 ℃, preserving heat for 0.5-1.5 h, and cooling to be less than or equal to 60 ℃;
b. adding melamine, heating to 65-85 ℃, and keeping the temperature for 0.5-1.5 h;
c. adding butyronitrile latex, heating to 80-105 ℃, and keeping the temperature for 0.2-0.8 h;
d. cooling to below 70 deg.C, adjusting pH to 7, and dehydrating.
The phenolic resin is a high molecular material obtained by condensation polymerization of phenol and formaldehyde, and the molecular structure of the phenolic resin contains a large number of rigid benzene rings, so that the material has good temperature resistance, dimensional stability and the like, but the product of the phenolic resin is poor in toughness and crisp in quality, and the application of the phenolic resin is limited.
The formaldehyde in this application is a commercially available aqueous formaldehyde solution with a concentration of 37% by weight.
In order to shorten the reaction time of phenol and formaldehyde in the preparation process, in some preferred embodiments, the pH is adjusted in the step a by using 10-30 wt% NaOH solution. In the application, NaOH solution is used as a catalyst for phenolic aldehyde polycondensation, and the catalyst interacts with reactant molecules to form an active carbanion intermediate compound, and then is decomposed into a product, so that the reaction efficiency is improved. When the adjusted pH is too low or the reaction temperature is too low, the reaction time is prolonged, and when the pH is too high or the reaction temperature is too high, the reaction is not easy to control.
In order to improve the toughness of the phenolic resin, in some preferred embodiments, the melamine is used in an amount of 5 to 20 wt% of the phenol. The melamine is introduced, so that the phenolic resin is toughened from a molecular structure, the rigid structure of the phenolic resin is disturbed, and the structural regularity is reduced, wherein the reaction equation is shown in figure 1. When the dosage of the melamine is too low, the toughening effect is insufficient, otherwise, when the dosage of the melamine is too high, the toughness of the material is not increased or decreased because the melamine is also in a ring structure.
In order to further improve the toughness of the phenolic resin, in some preferred embodiments, the butyronitrile latex is used in an amount of 1 to 30 wt% of phenol; further preferably, the butyronitrile latex is carboxyl butyronitrile latex; further, the carboxylic acrylonitrile butadiene latex is terminal carboxylic acrylonitrile butadiene latex. the-COOH in the carboxyl-terminated butyronitrile latex reacts with-OH in the phenolic resin to form ester bonds, so that flexible chain segments such as carbon-carbon double bonds, carbon-carbon bonds and the like are added on a molecular chain of the phenolic resin to balance the rigidity of the structure. When the amount of the butyronitrile latex is too small, the change of the whole structure of the material is small, and otherwise, when the amount is too large, the properties of the phenolic resin such as dimensional stability and the like are reduced.
The carboxyl-terminated butyronitrile latex is purchased from Jinan Brightness chemical Co., Ltd, and is of a brand of FM-21, and the content of acrylonitrile is 25-45 wt%.
In addition, melamine and nitrile rubber contain a flame-retardant nitrogen element, so that the flame retardant property of the phenolic resin can be remarkably improved, and the application range of the resin is expanded.
In some preferred embodiments, hydrochloric acid is used to adjust the pH in step d. Hydrochloric acid in the present application means a hydrochloric acid having a volume ratio of 1: concentrated hydrochloric acid (commercially available, 38% strength by weight) of 1 was mixed with water to give a hydrochloric acid solution.
The second aspect of the present invention provides a modified phenolic resin prepared using the preparation method as described above.
The third aspect of the invention provides a preparation method of modified phenolic foam, which comprises the following steps: and adding the surfactant, the foaming agent and the curing agent into the modified phenolic resin, stirring, pouring into a mould, and curing to obtain the modified phenolic resin.
In some preferred embodiments, the surfactant is used in an amount of 1 to 20 wt% of the modified phenolic resin; further preferably, the surfactant is selected from one or more of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, tween 80, tween 60, span 80, span 60, lecithin and monoglyceride; further, the surfactant is tween 80. The surfactant can change the surface/interface property of the solution to form a stable system, and the Tween 80, also called polyoxyethylene sorbitan monooleate, can disperse the resin solution into stable emulsion and improve the uniformity of the phenolic resin foam.
In some preferred embodiments, the amount of the foaming agent is 1 to 20 wt% of the modified phenolic resin; further preferably, the foaming agent is selected from one or more of n-pentane, n-hexane, n-heptane, petroleum ether and trichlorofluoromethane; further, the blowing agent is n-pentane. N-pentane is used as a foaming agent, and the n-pentane continuously volatilizes in the curing process to leave a large number of bubbles, so that the foam material is obtained. When the amount of the foaming agent is too much, the apparent density of the phenolic foam is reduced, and the strength is greatly reduced, whereas when the amount is too little, the foaming effect is poor, and the heat insulation performance of the material is poor.
In some preferred embodiments, the amount of the curing agent is 5 to 35 wt% of the modified phenolic resin; more preferably, the curing agent is a mixture of p-toluenesulfonic acid, phosphoric acid and water, and the weight ratio is (1-5): 1: (1-5). The curing agent is added in the foaming process, so that the phenolic resin is cured and crosslinked under an acidic condition, the crosslinking reaction can be adjusted by using the mixed acid in a certain proportion, fine and uniform foam pores are obtained by matching with the foaming, the foam pores are stronger in compressive stress bearing capacity and deformation capacity and more stable by matching with the structure of the phenolic resin, and broken pores are reduced.
In some preferred embodiments, the method for preparing the modified phenolic foam comprises the following steps: adding the surfactant, the foaming agent and the curing agent into the modified phenolic resin, stirring, pouring into a mould, and keeping the temperature at 75 ℃ for curing to obtain the modified phenolic resin.
In a fourth aspect, the present invention provides a modified phenolic foam prepared using the preparation method as described above.
Examples
The technical solution of the present invention is described in detail by the following examples, but the scope of the present invention is not limited to the examples. Unless otherwise specified, the starting materials in the present invention are all commercially available.
Example 1
Embodiment 1 provides a method for preparing a modified phenolic resin, comprising the following steps: melting 94g of phenol, adding the phenol into a reaction kettle, adding 150mL of 37 wt% formaldehyde aqueous solution, adding 10 wt% sodium hydroxide solution at 45 ℃, adjusting the pH to 8-9, heating to 80 ℃, keeping the temperature for 1h, and cooling to 58 ℃ to obtain phenolic resin; adding 9.4g melamine, heating to 80 deg.C and maintaining for 1h, adding 0.94g carboxyl-terminated butyronitrile latex (available from Jinnan Bright chemical Co., Ltd., under the brand name FM-21), heating to 95 deg.C and maintaining for 0.5h, cooling to 60 deg.C, neutralizing with hydrochloric acid until pH is 7, and dehydrating.
The embodiment also provides a preparation method of the modified phenolic foam, which comprises the following steps: adding 1.8g of Tween 80, 4g of n-pentane and 3.6g of curing agent into 30g of the modified phenolic resin, stirring, pouring into a mold, and carrying out heat preservation and curing at 75 ℃ for 2 hours to obtain the modified phenolic resin; the curing agent is prepared from the following components in percentage by weight of 1: 1: 2, p-toluenesulfonic acid, phosphoric acid and water.
Example 2
Embodiment 2 provides a method for preparing a modified phenolic resin, comprising the following steps: melting 94g of phenol, adding the phenol into a reaction kettle, adding 150mL of 37 wt% formaldehyde aqueous solution, adding 20 wt% sodium hydroxide solution at 45 ℃, adjusting the pH to 8-9, heating to 82 ℃ and keeping for 1h, and cooling to 60 ℃ to obtain phenolic resin; adding 2.82g melamine, heating to 76 deg.C and maintaining for 1h, adding 2.35g carboxyl-terminated butyronitrile latex (available from Jinnan Bright chemical Co., Ltd., under the brand name FM-21), heating to 97 deg.C and maintaining for 0.5h, cooling to 60 deg.C, neutralizing with hydrochloric acid until pH is 7, and dehydrating.
The embodiment also provides a preparation method of the modified phenolic foam, which comprises the following steps: adding 1.8g of Tween 80, 3.6g of n-pentane and 3.6g of curing agent into 30g of the modified phenolic resin, stirring, pouring into a mold, and keeping the temperature at 75 ℃ for curing for 2 hours to obtain the modified phenolic resin; the curing agent is prepared from the following components in percentage by weight: 1: 1, p-toluenesulfonic acid, phosphoric acid and water.
Example 3
Embodiment 3 provides a method for preparing a modified phenolic resin, comprising the following steps: melting 94g of phenol, adding the phenol into a reaction kettle, adding 150mL of 37 wt% formaldehyde aqueous solution, adding 20 wt% sodium hydroxide solution at 45 ℃, adjusting the pH to 8-9, heating to 81 ℃, keeping the temperature for 1h, and cooling to 58 ℃ to obtain phenolic resin; adding 14.1g melamine, heating to 77 deg.C and maintaining for 1h, adding 4.7g carboxyl-terminated butyronitrile latex (available from Jinnan Bright chemical Co., Ltd., under the brand name FM-21), heating to 98 deg.C and maintaining for 0.5h, cooling to 60 deg.C, neutralizing with hydrochloric acid until pH is 7, and dehydrating.
The embodiment also provides a preparation method of the modified phenolic foam, which comprises the following steps: adding 1.8g of Tween 80, 4g of n-pentane and 3.6g of curing agent into 30g of the modified phenolic resin, stirring, pouring into a mold, and carrying out heat preservation and curing at 75 ℃ for 2 hours to obtain the modified phenolic resin; the curing agent is prepared from the following components in percentage by weight of 3: 1: 2, p-toluenesulfonic acid, phosphoric acid and water.
Example 4
Embodiment 4 provides a method for preparing a modified phenolic resin, comprising the following steps: melting 94g of phenol, adding the phenol into a reaction kettle, adding 150mL of 37 wt% formaldehyde aqueous solution, adding 20 wt% sodium hydroxide solution at 45 ℃, adjusting the pH to 8-9, heating to 83 ℃ and keeping for 1h, and cooling to 58 ℃ to obtain phenolic resin; adding 3.76g melamine, heating to 78 deg.C and maintaining for 1h, adding 9.4g carboxyl-terminated butyronitrile latex (available from Jinnan Bright chemical Co., Ltd., under the brand name FM-21), heating to 100 deg.C and maintaining for 0.5h, cooling to 60 deg.C, neutralizing with hydrochloric acid until pH is 7, and dehydrating.
The embodiment also provides a preparation method of the modified phenolic foam, which comprises the following steps: adding 1.8g of Tween 80, 4g of n-pentane and 3.6g of curing agent into 30g of the modified phenolic resin, stirring, pouring into a mold, and carrying out heat preservation and curing at 75 ℃ for 2 hours to obtain the modified phenolic resin; the curing agent is prepared from the following components in percentage by weight: 1: 3, p-toluenesulfonic acid, phosphoric acid and water.
Example 5
Embodiment 5 provides a method for preparing a modified phenolic resin, comprising the steps of: melting 94g of phenol, adding the phenol into a reaction kettle, adding 150mL of 37 wt% formaldehyde aqueous solution, adding 20 wt% sodium hydroxide solution at 45 ℃, adjusting the pH to 8-9, heating to 85 ℃, keeping the temperature for 1h, and cooling to 58 ℃ to obtain phenolic resin; adding 7.52g melamine, heating to 80 deg.C and maintaining for 1h, adding 14.1g carboxyl-terminated butyronitrile latex (available from Jinnan Bright chemical Co., Ltd., under the brand name FM-21), heating to 102 deg.C and maintaining for 0.5h, cooling to 60 deg.C, neutralizing with hydrochloric acid to pH 7, and dehydrating.
The embodiment also provides a preparation method of the modified phenolic foam, which comprises the following steps: adding 1.8g of Tween 80, 4g of n-pentane and 3.6g of curing agent into 30g of the modified phenolic resin, stirring, pouring into a mold, and carrying out heat preservation and curing at 75 ℃ for 2 hours to obtain the modified phenolic resin; the curing agent is prepared from the following components in percentage by weight of 4: 1: 1, p-toluenesulfonic acid, phosphoric acid and water.
Comparative example 1
Comparative example 1 provides a method of preparing a phenolic resin comprising the steps of: melting 94g of phenol, adding the phenol into a reaction kettle, adding 150mL of 37 wt% formaldehyde aqueous solution, adding 10 wt% sodium hydroxide solution at 45 ℃, adjusting the pH to 8-9, heating to 80 ℃, keeping the temperature for 1h, cooling to 60 ℃, neutralizing with hydrochloric acid until the pH is 7, and dehydrating to obtain the phenol formaldehyde resin.
The embodiment also provides a preparation method of the phenolic foam, which comprises the following steps: adding 1.8g of Tween 80, 4g of n-pentane and 3.6g of curing agent into 30g of the phenolic resin, stirring, pouring into a mold, and keeping the temperature at 75 ℃ for curing for 2 hours to obtain the phenolic resin; the curing agent is prepared from the following components in percentage by weight of 1: 1: 2, p-toluenesulfonic acid, phosphoric acid and water.
Comparative example 2
Comparative example 2 provides a method of preparing a phenolic resin comprising the steps of: melting 94g of phenol, adding the phenol into a reaction kettle, adding 150mL of 37 wt% formaldehyde aqueous solution, adding 20 wt% sodium hydroxide solution at 45 ℃, adjusting the pH to 8-9, heating to 82 ℃ and keeping for 1h, cooling to 60 ℃, neutralizing with hydrochloric acid until the pH is 7, and dehydrating to obtain the phenol formaldehyde resin.
The embodiment also provides a preparation method of the phenolic foam, which comprises the following steps: adding 1.8g of Tween 80, 3.6g of n-pentane and 3.6g of curing agent into 30g of the phenolic resin, stirring, pouring into a mold, and keeping the temperature at 75 ℃ for curing for 2 hours to obtain the phenolic resin; the curing agent is prepared from the following components in percentage by weight: 1: 1, p-toluenesulfonic acid, phosphoric acid and water.
Comparative example 3
Comparative example 3 provides a method of preparing a phenolic resin comprising the steps of: melting 94g of phenol, adding the phenol into a reaction kettle, adding 150mL of 37 wt% formaldehyde aqueous solution, adding 20 wt% sodium hydroxide solution at 45 ℃, adjusting the pH to 8-9, heating to 81 ℃ and keeping for 1h, cooling to 60 ℃, neutralizing with hydrochloric acid until the pH is 7, and dehydrating to obtain the phenol formaldehyde resin.
The embodiment also provides a preparation method of the phenolic foam, which comprises the following steps: adding 1.8g of Tween 80, 4g of n-pentane and 3.6g of curing agent into 30g of the phenolic resin, stirring, pouring into a mold, and keeping the temperature at 75 ℃ for curing for 2 hours to obtain the phenolic resin; the curing agent is prepared from the following components in percentage by weight of 3: 1: 2, p-toluenesulfonic acid, phosphoric acid and water.
Comparative example 4
Comparative example 4 provides a method of preparing a phenolic resin comprising the steps of: melting 94g of phenol, adding the phenol into a reaction kettle, adding 150mL of 37 wt% formaldehyde aqueous solution, adding 20 wt% sodium hydroxide solution at 45 ℃, adjusting the pH to 8-9, heating to 83 ℃ and keeping for 1h, cooling to 60 ℃, neutralizing with hydrochloric acid until the pH is 7, and dehydrating to obtain the phenol formaldehyde resin.
The embodiment also provides a preparation method of the phenolic foam, which comprises the following steps: adding 1.8g of Tween 80, 4g of n-pentane and 3.6g of curing agent into 30g of the phenolic resin, stirring, pouring into a mold, and keeping the temperature at 75 ℃ for curing for 2 hours to obtain the phenolic resin; the curing agent is prepared from the following components in percentage by weight: 1: 3, p-toluenesulfonic acid, phosphoric acid and water.
Comparative example 5
Comparative example 5 provides a method of preparing a phenolic resin comprising the steps of: melting 94g of phenol, adding the phenol into a reaction kettle, adding 150mL of 37 wt% formaldehyde aqueous solution, adding 20 wt% sodium hydroxide solution at 45 ℃, adjusting the pH to 8-9, heating to 85 ℃ and keeping for 1h, cooling to 60 ℃, neutralizing with hydrochloric acid until the pH is 7, and dehydrating to obtain the phenol formaldehyde resin.
The embodiment also provides a preparation method of the phenolic foam, which comprises the following steps: adding 1.8g of Tween 80, 4g of n-pentane and 3.6g of curing agent into 30g of the phenolic resin, stirring, pouring into a mold, and keeping the temperature at 75 ℃ for curing for 2 hours to obtain the phenolic resin; the curing agent is prepared from the following components in percentage by weight of 4: 1: 1, p-toluenesulfonic acid, phosphoric acid and water.
Evaluation of Performance
1. The results of visual observation of the first modified phenolic resin and the modified phenolic foam obtained in examples 1 to 5 are shown in fig. 2.
2. And (3) oxygen index determination: the modified phenolic foams obtained in examples 1 to 5 and the phenolic foams obtained in comparative examples 1 to 5 were tested for their oxygen index using an oxygen index meter as shown in fig. 3, and the results are shown in table 1 and fig. 4.
TABLE 1
Examples 1 2 3 4 5
Oxygen index (%) 45.3 44.2 43.3 45.3 44.2
Comparative example 1 2 3 4 5
Oxygen index (%) 35.0 34.0 34.0 32.0 31.0
From the oxygen index curves, it can be seen that the modified phenolic foam has a significant increase in oxygen index of 45% compared to the unmodified phenolic foam.
3. And (3) testing mechanical properties: the phenolic foams obtained in examples 1 to 5 and comparative example 1 were subjected to bending strength test and impact strength test using a microcomputer-controlled electronic universal tester, and the results are shown in table 2 and fig. 5.
TABLE 2
Phenolic foam samples Flexural modulus (MPa) Flexural Strength (MPa) Impact strength (kJ/m)2)
Comparative example 1 1.623 0.0 0.14
Example 1 2.021 0.1 0.26
Example 2 3.654 0.1 0.35
Example 3 4.332 0.1 0.85
Example 4 5.421 0.1 1.39
Example 5 7.973 0.1 1.55
The mechanical property characterization shows that the mechanical property of the modified phenolic foam is well improved, so that the flexural modulus of the phenolic foam is improved by about 5 times, and the impact strength is improved by 10 times.
4. Foam morphology: the phenolic foam was microscopically photographed using a scanning electron microscope, model Hitachi 3030.
FIG. 6 is a scanning electron microscope image at 100 times, and it can be seen from the image that the modified phenolic foams (examples 1-5, fig. a, b, c, d, e) have higher cell closing rate than the unmodified phenolic foams (comparative example 1, fig. f), and the slag on the cross section on the image is also reduced significantly, thus proving that the addition of the modified phenolic foams can improve the condition that the cells are easy to break, thereby improving the performance of the foams.
FIG. 7 is a scanning electron microscope image at 500 Xfrom which it can be seen that the reduction in cell breakage in the fields of views a, b, c, d, e is seen in comparison to the cells of the unmodified image f (comparative example 1), demonstrating that the nitrile latex and melamine composite modified foam reduces well the cell breakage at break.
The analysis can show that the modification of the phenolic foam can greatly improve the performance of the phenolic foam in the toughness aspect and also improve the regularity of the foam holes and the appearance of the foam holes to a certain extent.
Finally, it should be understood that the above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. The preparation method of the modified phenolic resin is characterized by comprising the following steps:
a. the mixing molar ratio is 1: (1-2) adjusting the pH value of phenol and formaldehyde to 8-10 at 40-45 ℃, heating to 75-90 ℃, preserving heat for 0.5-1.5 h, and cooling to be less than or equal to 60 ℃;
b. adding melamine, heating to 65-85 ℃, and keeping the temperature for 0.5-1.5 h;
c. adding butyronitrile latex, heating to 80-105 ℃, and keeping the temperature for 0.2-0.8 h;
d. cooling to below 70 deg.C, adjusting pH to 7, and dehydrating.
2. The method for preparing the modified phenolic resin according to claim 1, wherein the pH is adjusted by using 10-30 wt% NaOH solution in the step a.
3. The method for preparing the modified phenolic resin according to claim 1, wherein the amount of the melamine is 5 to 20 wt% of the phenol.
4. The method for preparing the modified phenolic resin according to claim 1, wherein the amount of the butyronitrile latex is 1-30 wt% of phenol.
5. The method for producing a modified phenolic resin according to any one of claims 1 to 4, wherein hydrochloric acid is used for adjusting the pH in the step d.
6. A modified phenolic resin, characterized in that it is produced by the production method according to any one of claims 1 to 5.
7. The preparation method of the modified phenolic foam is characterized by comprising the following steps: adding the surfactant, the foaming agent and the curing agent into the modified phenolic resin as claimed in claim 6, stirring, pouring into a mold, and curing to obtain the modified phenolic resin.
8. The method for preparing the modified phenolic foam according to claim 7, wherein the amount of the surfactant is 1 to 20 wt% of the modified phenolic resin.
9. The method for preparing the modified phenolic foam according to claim 7, wherein the amount of the foaming agent is 1-20 wt% of the modified phenolic resin.
10. A modified phenolic foam, characterized in that it is produced by the production method according to any one of claims 7 to 9.
CN202010296010.XA 2020-04-15 2020-04-15 Preparation method of modified phenolic resin and foam and prepared product Pending CN111349204A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105315612A (en) * 2015-11-06 2016-02-10 芜湖市伟华泡塑有限公司 High-inflaming-retarding modified phenolic resin foamed plastic and preparation method thereof
CN108467567A (en) * 2018-04-13 2018-08-31 武汉工程大学 A kind of preparation method of melamine/polyurethane toughened phenol formaldehyde foam

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105315612A (en) * 2015-11-06 2016-02-10 芜湖市伟华泡塑有限公司 High-inflaming-retarding modified phenolic resin foamed plastic and preparation method thereof
CN108467567A (en) * 2018-04-13 2018-08-31 武汉工程大学 A kind of preparation method of melamine/polyurethane toughened phenol formaldehyde foam

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* Cited by examiner, † Cited by third party
Title
宋光等: "液体NBR增韧酚醛泡沫研究", 《塑料工业》 *

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