CN106433016B - Preparation method of modified enhanced heat-preservation sound-insulation phenolic foam board - Google Patents

Preparation method of modified enhanced heat-preservation sound-insulation phenolic foam board Download PDF

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CN106433016B
CN106433016B CN201610759888.6A CN201610759888A CN106433016B CN 106433016 B CN106433016 B CN 106433016B CN 201610759888 A CN201610759888 A CN 201610759888A CN 106433016 B CN106433016 B CN 106433016B
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parts
modified
die
foam board
phenolic foam
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CN106433016A (en
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范平一
郑新宇
张圣华
张明芬
吴丹
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NANTONG ZHONGBAO ENERGY SAVING TECHNOLOGY Co.,Ltd.
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Nantong Zhongbao Energy Saving Technology Co ltd
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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
    • C08L61/14—Modified phenol-aldehyde condensates
    • 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
    • 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
    • C08J9/06—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 chemical blowing agent
    • C08J9/10—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 chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
    • C08J9/107—Nitroso compounds
    • 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
    • C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
    • 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
    • C08J2361/14—Modified phenol-aldehyde condensates
    • 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
    • C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2471/02—Polyalkylene oxides
    • 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
    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2483/04—Polysiloxanes
    • 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
    • C08L2203/00—Applications
    • C08L2203/14—Applications used for foams
    • 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
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Abstract

The invention discloses a modified enhanced heat-preservation sound-insulation phenolic foam board and a preparation method thereof, wherein the modified enhanced heat-preservation sound-insulation phenolic foam board comprises the following components in parts by weight: 100 parts of modified phenolic resin, 10-30 parts of modified clay, 1-10 parts of toughening agent, 1-5 parts of stabilizer, 10-20 parts of foaming agent, 2-10 parts of surfactant, 5-10 parts of flame retardant and 5-20 parts of curing agent. The preparation method of the modified enhanced heat-preservation sound-insulation phenolic foam board comprises the following steps: 1) preparing modified phenolic resin; 2) conveying the modified phenolic resin, the modified clay and the toughening agent into a mixing head of a pouring foaming machine by using a metering pump, sequentially adding a stabilizer, a foaming agent, a surfactant and a flame retardant, uniformly stirring, and then adding a curing agent for stirring; 3) foaming and curing in the film cavity. The invention greatly improves the toughness, fire resistance and sound insulation performance of the phenolic foam by improving the composite production process.

Description

Preparation method of modified enhanced heat-preservation sound-insulation phenolic foam board
Technical Field
The invention relates to a preparation method of a modified enhanced heat-preservation sound-insulation phenolic foam board, belonging to the field of preparation of building heat-preservation sound-insulation materials.
Background
Compared with the traditional polyethylene foam and polyurethane foam board, the phenolic foam has low heat conductivity coefficient, flame retardancy which the two foams do not have, and the combustion grade reaches B1 grade, so that the phenolic foam has excellent flame retardant property, is an ideal flame retardant material, and is widely applied to heat preservation and fire retardation occasions. Meanwhile, the phenolic foam board is used as a light foam board, and due to the specific cellular structure of the phenolic foam board, the phenolic foam board is suitable for both the thermal insulation performance and the sound insulation performance. Therefore, the heat preservation, sound insulation and flame retardant properties of the phenolic foam board are applied to building walls and floors for popularization, and the phenolic foam board has good market prospect.
The sound insulation foam board with improved performance is also available in the market, but the common foam sound insulation board only uses the patterns on the surface of the aluminum foil to be combined with the phenolic foam board to form the grooves for sound insulation, or uses the prepared phenolic foam board to be secondarily processed to form the grooves of the wavy lines for sound insulation, and compared with the simple foam hole sound insulation, the sound insulation effect is improved, but a large promotion space is provided. And the brittleness and the cost of the phenolic foam plate also limit the popularization and the application of the phenolic foam plate as a heat insulation material.
In order to improve the toughness, impact resistance and sound insulation effect of the foam on the basis of keeping the excellent flame retardant property of the phenolic foam, prepare the phenolic foam with low price and excellent comprehensive performance, the phenolic foam is modified and researched by selecting different modifiers and production processes.
Disclosure of Invention
The invention provides a modified enhanced heat-preservation sound-insulation phenolic foam board which is improved on the basis of the original production process, has the advantages of simple process and easiness in operation, and can improve the sound insulation effect, the flame retardance, the impact resistance and the slag dropping prevention rate, and a preparation method thereof, aiming at overcoming the defects of poor toughness, low cohesive energy, high slag dropping rate, low mechanical strength and general sound insulation effect of the phenolic foam board in the existing market.
The invention is realized by the following technical scheme:
the modified enhanced heat-preservation sound-insulation phenolic foam board comprises the following components in parts by weight: 100 parts of modified phenolic resin, 10-30 parts of modified clay, 1-10 parts of toughening agent, 1-5 parts of stabilizer, 10-20 parts of foaming agent, 2-10 parts of surfactant, 5-10 parts of flame retardant and 5-20 parts of curing agent.
The preparation method of the modified enhanced heat-preservation sound-insulation phenolic foam board comprises the following steps:
1) preparing modified phenolic resin: preparing phenol, paraformaldehyde, NaOH and ammonia water, wherein the proportion of the phenol to the paraformaldehyde is 1 (1.5-2.0), the amount of the NaOH is 3% -6% of that of the phenol, and the amount of the ammonia water is 1% -3% of that of the phenol; mixing NaOH and ammonia water, adding 80% of the total amount of a mixed solution of the NaOH and the ammonia water into phenol, mixing, preserving heat for 20-40min at 40-60 ℃, adding 80% of the total amount of paraformaldehyde, preserving heat for 20-40min at 60-70 ℃, then adding the rest of the mixed solution of the NaOH and the ammonia water, preserving heat for 10-20min, adding the rest of paraformaldehyde, adjusting the pH value to 8-9, adding a modifier, heating to 70-80 ℃, preserving heat for 10-20min, refluxing for 30-60min at 85-95 ℃, and discharging by decompression and dehydration; the modifier in the step 1) is epoxy resin E51;
2) conveying the modified phenolic resin, the modified clay and the toughening agent prepared in the step 1) into a mixing head of a pouring foaming machine by using a metering pump, sequentially adding a stabilizer, a foaming agent, a surfactant and a flame retardant, uniformly stirring, and then adding a curing agent for stirring; the toughening agent used in the step 2) is any one of ethylene glycol, dioctyl phthalate and tricresyl phosphate;
3) rapidly pouring the stirred material into a die cavity covered with a protective layer from the upper part of a pouring foaming machine, covering an upper cover plate of the die by a mechanical arm for die pressing, wherein cylindrical bosses which are regularly and orderly arranged are arranged at the bottom of the cover plate, feeding the die and the cover plate into a laminating conveyor, foaming, curing and forming the material between a bottom surface material and the upper cover plate in the die, and conveying the material forwards along with the laminating conveyor, wherein the temperature in the die is controlled to be 65-70 ℃ in the conveying process, the conveying time is 15-20 minutes, the depth of the die is 20-30 mm, the height of the bosses on the die is 3-4mm, and the bottom surface material in the die is high-strength non-woven fabric;
4) and cooling and demolding the cured phenolic foam board.
In a further development of the invention, the blowing agent is dinitrosopentamethylenetetramine, a fluorine-free blowing agent.
The invention is further improved in that the surfactant is fatty alcohol polyoxyethylene, polyoxypropylene ether, an addition product of nonylphenol and ethylene oxide, or a block copolymer of polysiloxane, polyoxyethylene and polyoxypropylene.
The further improvement of the invention is that the curing agent is a mixture of inorganic acid and organic acid, the inorganic acid can be one of sulfuric acid, hydrochloric acid and phosphoric acid, and the organic acid is one of oxalic acid, adipic acid, benzene nitric acid, phenol nitric acid, toluene sulfonic acid, benzene sulfonic acid and petroleum sulfonic acid, and is added into the prepared aqueous solution with the concentration of 40-60%.
In a further improvement of the invention, the stabilizer is a mixture of tween-80 and methyl silicone oil.
The invention further improves that the flame retardant is inorganic flame retardant zinc borate.
The invention has the following beneficial effects:
the production method is characterized in that a traditional phenolic foam insulation board production line is improved in tooling, phenolic resin is foamed in a film cavity of a die, one surface of a produced phenolic foam board is compounded with a protective film, and the other surface of the produced phenolic foam board is pressed by a cover plate film on the die to form a circular cavity; the processing thickness of the foam board is 30mm and 20mm, the depth of the cavity is only 3-4mm, and the load-bearing and pressure-resisting capacity of the phenolic foam board cannot be affected.
The modifier is added into the modified phenolic resin before reflux, so that the epoxy resin is dissolved favorably, is fully contacted with a reaction system, is reacted completely, is uniform in solution, is reacted with the phenolic resin and is grafted into phenolic resin molecules, so that the product is branched, the molecular weight is increased, the tensile-shear strength is increased, and the flexibility is improved; the surfactant is one of fatty alcohol polyoxyethylene, polyoxyethylene polyoxypropylene ether, nonyl phenol and ethylene oxide adduct or block copolymer of polysiloxane, polyoxyethylene and polyoxypropylene, and has good foam stability and strong emulsification effect. According to the invention, through the compounding of materials and the improvement of a production process, the phenolic foam board has fine and smooth foam holes, uniform density and reliable strength and heat insulation performance, and the toughness, flame retardance and sound insulation performance of the phenolic foam are greatly improved.
Detailed Description
The present invention is further illustrated by the following examples.
Example 1
The preparation method of the modified enhanced heat-preservation sound-insulation phenolic foam board comprises the following steps:
1) preparing modified phenolic resin: preparing phenol, paraformaldehyde, NaOH and ammonia water, wherein the proportion of the phenol to the paraformaldehyde is 1 (1.5-2.0), the amount of the NaOH is 3% -6% of that of the phenol, and the amount of the ammonia water is 1% -3% of that of the phenol; mixing NaOH and ammonia water, adding 80% of the total amount of a mixed solution of the NaOH and the ammonia water into phenol, mixing, preserving heat for 20-40min at 40-60 ℃, adding 80% of the total amount of paraformaldehyde, preserving heat for 20-40min at 60-70 ℃, then adding the rest of the mixed solution of the NaOH and the ammonia water, preserving heat for 10-20min, adding the rest of paraformaldehyde, adjusting the pH value to 8-9, adding a modifier, heating to 70-80 ℃, preserving heat for 10-20min, refluxing for 30-60min at 85-95 ℃, and discharging by decompression and dehydration; the modifier in the step 1) is epoxy resin E51;
2) conveying the modified phenolic resin, the modified clay and the toughening agent prepared in the step 1) into a mixing head of a pouring foaming machine by using a metering pump, sequentially adding a stabilizer, a foaming agent, a surfactant and a flame retardant, uniformly stirring, and then adding a curing agent for stirring; the toughening agent used in the step 2) is any one of ethylene glycol, dioctyl phthalate and tricresyl phosphate;
3) rapidly pouring the stirred material into a die cavity covered with a protective layer from the upper part of a pouring foaming machine, covering an upper cover plate of the die by a mechanical arm for die pressing, wherein cylindrical bosses which are regularly and orderly arranged are arranged at the bottom of the cover plate, feeding the die and the cover plate into a laminating conveyor, foaming, curing and forming the material between a bottom surface material and the upper cover plate in the die, and conveying the material forwards along with the laminating conveyor, wherein the temperature in the die is controlled to be 65-70 ℃ in the conveying process, the conveying time is 15-20 minutes, the depth of the die is 20-30 mm, the height of the bosses on the die is 3-4mm, and the bottom surface material in the die is high-strength non-woven fabric;
4) and cooling and demolding the cured phenolic foam board.
The mass fraction of the raw materials in the steps is as follows:
100 parts of modified phenolic resin prepared in the step 1, 10 parts of modified clay, 1 part of toughening agent, 1 part of stabilizer, 10 parts of foaming agent, 2 parts of surfactant, 5 parts of flame retardant and 5 parts of curing agent.
Example 2
The preparation method is as in example 1, and the components in parts by weight are as follows: 100 parts of modified phenolic resin, 30 parts of modified clay, 10 parts of toughening agent, 5 parts of stabilizing agent, 20 parts of foaming agent, 10 parts of surfactant, 10 parts of flame retardant and 20 parts of curing agent.
Example 3
The preparation method is as in example 1, and the components in parts by weight are as follows: 100 parts of modified phenolic resin, 20 parts of modified clay, 1 part of toughening agent, 5 parts of stabilizing agent, 10 parts of foaming agent, 2 parts of surfactant, 10 parts of flame retardant and 5 parts of curing agent.
Example 4
The preparation method is as in example 1, and the components in parts by weight are as follows: 100 parts of modified phenolic resin, 15 parts of modified clay, 10 parts of toughening agent, 1 part of stabilizer, 20 parts of foaming agent, 10 parts of surfactant, 5 parts of flame retardant and 10 parts of curing agent.
Example 5
The preparation method is as in example 1, and the components in parts by weight are as follows: 100 parts of modified phenolic resin, 25 parts of modified clay, 7 parts of toughening agent, 3 parts of stabilizing agent, 15 parts of foaming agent, 5 parts of surfactant, 7 parts of flame retardant and 18 parts of curing agent.
Example 6
The preparation method is as in example 1, and the components in parts by weight are as follows: 100 parts of modified phenolic resin, 20 parts of modified clay, 3 parts of toughening agent, 5 parts of stabilizing agent, 15 parts of foaming agent, 10 parts of surfactant, 6 parts of flame retardant and 15 parts of curing agent.
The properties of the modified reinforced thermal insulation and sound insulation phenolic foam boards obtained in the embodiments 1-6 are shown in Table 1.
TABLE 1 Properties of phenolic foam boards
As can be seen from Table 1, the modified enhanced heat-insulating sound-insulating phenolic foam board prepared by the invention has good heat-insulating and pressure-resisting effects and greatly improved toughness. The noise reduction effect of the invention is obviously improved on the surface of the structure through the detection of the sound insulation effect.
The above description is for the purpose of illustrating embodiments of the invention and is not intended to limit the invention, and it will be understood by those skilled in the art that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (3)

1. The preparation method of the modified enhanced heat-preservation sound-insulation phenolic foam board is characterized in that the modified enhanced heat-preservation sound-insulation phenolic foam board comprises the following components in parts by weight: 100 parts of modified phenolic resin, 10-30 parts of modified clay, 1-10 parts of toughening agent, 1-5 parts of stabilizer, 10-20 parts of foaming agent, 2-10 parts of surfactant, 5-10 parts of flame retardant and 5-20 parts of curing agent;
the preparation method comprises the following steps:
1) preparing modified phenolic resin: preparing phenol, paraformaldehyde, NaOH and ammonia water, wherein the proportion of the phenol to the paraformaldehyde is 1 (1.5-2.0), the amount of the NaOH is 3% -6% of that of the phenol, and the amount of the ammonia water is 1% -3% of that of the phenol; mixing NaOH and ammonia water, adding 80% of the total amount of NaOH and ammonia water mixed solution into phenol and a modifier, mixing, preserving heat for 20-40min at 40-60 ℃, adding 80% of the total amount of paraformaldehyde, preserving heat for 20-40min at 60-70 ℃, then adding the rest of NaOH and ammonia water mixed solution, preserving heat for 10-20min, adding the rest of paraformaldehyde, adjusting the pH value to 8-9, adding the modifier, heating to 70-80 ℃, preserving heat for 10-20min, refluxing for 30-60min at 85-95 ℃, and discharging by means of reduced pressure dehydration; the modifier in the step 1) is epoxy resin E51;
2) conveying the modified phenolic resin, the modified clay and the toughening agent prepared in the step 1) into a mixing head of a pouring foaming machine by using a metering pump, sequentially adding a stabilizer, a foaming agent, a surfactant and a flame retardant, uniformly stirring, and then adding a curing agent for stirring; wherein the toughening agent is ethylene glycol;
3) rapidly pouring the stirred material into a die cavity covered with a protective layer from the upper part of a pouring foaming machine, covering an upper cover plate of the die by a mechanical arm for die pressing, wherein cylindrical bosses which are regularly and orderly arranged are arranged at the bottom of the cover plate, feeding the die and the cover plate into a laminating conveyor, foaming, curing and forming the material between a bottom surface material and the upper cover plate in the die, and conveying the material forwards along with the laminating conveyor, wherein the temperature in the die is controlled to be 65-70 ℃ in the conveying process, the conveying time is 15-20 minutes, the depth of the die is 20-30 mm, the height of the bosses on the die is 3-4mm, and the bottom surface material in the die is high-strength non-woven fabric;
4) cooling and demoulding the cured phenolic foam board;
the foaming agent is a fluorine-free foaming agent dinitrosopentamethylenetetramine;
the surfactant is an addition product of nonyl phenol and ethylene oxide, or block copolymerization of polysiloxane, polyoxyethylene and polyoxypropylene;
the curing agent is a mixture of inorganic acid and organic acid, the inorganic acid is one of sulfuric acid, hydrochloric acid and phosphoric acid, and the organic acid is one of oxalic acid, adipic acid, benzene nitric acid, phenol nitric acid, toluene sulfonic acid, benzene sulfonic acid and petroleum sulfonic acid.
2. The modified enhanced thermal insulation and sound insulation phenolic foam board as claimed in claim 1, wherein the stabilizer is a mixture of tween-80 and methyl silicone oil.
3. The modified enhanced thermal insulation and sound insulation phenolic foam board as claimed in claim 1, wherein the flame retardant is inorganic flame retardant zinc borate.
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CN107325482B (en) * 2017-08-04 2019-04-09 国网山东省电力公司临沂供电公司 The method of the high-intensitive prefabricated cabin of integrated type foaming preparation
CN109486096A (en) * 2018-09-04 2019-03-19 徐州市华天塑业有限公司 A kind of novel sound insulating high temperature resistant foam board
CN110916945A (en) * 2019-11-04 2020-03-27 厦门市妇幼保健院（厦门市计划生育服务中心） Intelligent temperature-control baby incubator
CN110894271A (en) * 2019-11-28 2020-03-20 上海应用技术大学 Method for preparing water-soluble phenolic resin by using composite catalyst

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CN203594119U (en) * 2013-11-06 2014-05-14 营口象圆新材料工程技术有限公司 Modified phenolic foam insulation board for building
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CN1428372A (en) * 2001-12-26 2003-07-09 广州擎天新材料研究开发有限公司 Phenolic foam plastic composite product and its production and forming process
CN1834152A (en) * 2006-03-21 2006-09-20 上海胜星树脂涂料有限公司 Method of preparing phenolic foam insulation material via foaming at normal temp
KR101116238B1 (en) * 2006-09-21 2012-03-07 (주)엘지하우시스 Interfloor noise proofing material and floor execution method using the same
CN102061059A (en) * 2010-12-22 2011-05-18 中国林业科学研究院林产化学工业研究所 Wood fiber reinforced inflaming retarding foam material and machining method thereof
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CN104558669A (en) * 2014-08-29 2015-04-29 霍山捷成科技发展有限公司 Preparation method of phenolic foam board

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