CN113956608A - Neutral low-thermal-conductivity phenolic foam material for building thermal insulation and preparation method thereof - Google Patents
Neutral low-thermal-conductivity phenolic foam material for building thermal insulation and preparation method thereof Download PDFInfo
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- CN113956608A CN113956608A CN202111230300.5A CN202111230300A CN113956608A CN 113956608 A CN113956608 A CN 113956608A CN 202111230300 A CN202111230300 A CN 202111230300A CN 113956608 A CN113956608 A CN 113956608A
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- 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
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- 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
- C08J9/0014—Use of organic additives
- C08J9/0023—Use of organic additives containing oxygen
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- 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
- C08J9/0066—Use of inorganic compounding ingredients
-
- 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
- C08J9/009—Use of pretreated compounding ingredients
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- 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
- C08J9/143—Halogen containing compounds
- C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
- C08J9/145—Halogen containing compounds containing carbon, halogen and hydrogen only only chlorine as halogen atoms
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- 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
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
- C08J2203/142—Halogenated saturated hydrocarbons, e.g. H3C-CF3
-
- 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
- C08J2203/18—Binary blends of expanding agents
- C08J2203/182—Binary blends of expanding agents of physical blowing agents, e.g. acetone and butane
-
- 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
Abstract
The invention discloses a neutral low-heat-conductivity phenolic foam material for building heat preservation and a preparation method thereof. The foaming raw material of the neutral low-heat-conductivity phenolic foam material contains an acidic neutralizer alkaline salt substance, which is helpful for neutralizing an acid curing catalyst, and meanwhile, the resin with low moisture content can reduce the addition amount of the acid curing catalyst, so that the acid release amount of the phenolic foam in the use process is reduced, and the corrosion degree of the phenolic foam on a metal material is weakened; compared with the phenolic foam material only added with the inorganic filler in the prior art, the phenolic foam material has the advantages that the addition amount of the inorganic filler and the acid curing catalyst in the neutral phenolic foam material foaming raw material is small, the thermal conductivity coefficient is low, and meanwhile, the negative influence of the inorganic filler on the thermal conductivity coefficient of the phenolic foam material is overcome due to the addition of the aerogel or other substances with ultralow thermal conductivity.
Description
Technical Field
The invention relates to the technical field of phenolic resin, in particular to a neutral low-heat-conductivity phenolic foam material for building heat preservation and a preparation method thereof.
Background
The phenolic foam heat-insulating material is closed-cell rigid foamed plastic prepared by adding an emulsifier, a foaming agent, a curing agent and other auxiliary agents into phenolic resin, and is a material with excellent performance of high-efficiency heat insulation and flame retardancy. It overcomes the defects of common foamed plastics such as inflammability, much smoke, deformation by heat and the like, and belongs to thermosetting materials.
Phenolic foam has been greatly developed in the last 90 s, is firstly valued by national military in English, American and the like, is used in the fields of aerospace and national defense and military industry, is then applied to places with strict fire protection requirements such as civil airplanes, ships, stations, oil wells and the like, and is gradually pushed to public and civil construction fields such as hospitals, sports facilities, buildings and houses. The heat-insulating material is widely applied to the fields of heat insulation of buildings, central air-conditioning ventilation pipelines, heat insulation of various pipelines or equipment and the like. Since phenolic foam contains an acid cure catalyst, the acidity is low and acid may be released from the foam upon exposure to a humid environment or rain. When a metal material is in contact with the phenolic foam, the metal may be susceptible to corrosion.
Disclosure of Invention
The invention aims to provide a neutral low-heat-conductivity phenolic foam material for building heat preservation and a preparation method thereof, wherein the corrosion degree of the phenolic foam material to metal materials is weakened.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: a neutral low-heat-conductivity phenolic foam material for building heat insulation is prepared from boron modified thermosetting phenolic resin, foaming agent, surfactant, acid curing catalyst, flame retardant and acid neutralizer.
Preferably, the foaming raw materials comprise, by weight, 100 parts of boron-modified thermosetting phenolic resin, 3-6 parts of surfactant, 5-20 parts of foaming agent, 3-6 parts of flame retardant, 5-15 parts of acid curing catalyst and 3-6 parts of acid neutralizer.
Preferably, the flame retardant is one or more of ammonium polyphosphate, melamine cyanurate, zinc phosphate, silica aerogel, tris (1-chloro-2-propyl) phosphate and hollow glass microspheres.
Preferably, the acid neutralizer is one or more of disodium hydrogen phosphate, potassium hydrogen tartrate, EDTA2Na, calcium propionate and calcium carbonate.
Preferably, the water content of the boron modified thermosetting phenolic resin is 3-10%, and the viscosity is 3000-10000 mPa & s.
Preferably, the acid curing catalyst is a mixture of an acid and an alcohol, wherein the acid is one or more of sulfuric acid, phosphoric acid, dimethylbenzenesulfonic acid, and phenolsulfonic acid; the alcohol is one or more of ethylene glycol, diethylene glycol, glycerol and dipropylene glycol.
Preferably, the blowing agent is one or more of methylene chloride, cyclopentane, n-pentane, n-hexane, n-butane, isopentane, and petroleum ether.
Preferably, the surfactant is one or more of polysiloxane, castor oil polyoxyethylene ether, polyoxypropylene, polytriopear ester and silane coupling agent.
The preparation method of the neutral low-heat-conductivity phenolic foam material for building heat preservation comprises the following steps: mixing the boron modified thermosetting phenolic resin, the foaming agent, the surfactant, the acid curing catalyst, the flame retardant and the acid neutralizing agent, uniformly stirring, and then foaming and curing to obtain the neutral low-thermal-conductivity phenolic foam material.
Preferably, the foaming curing temperature is 60-80 ℃, and the foaming curing time is 5-30 min.
Compared with the prior art, the invention has the advantages that:
the foaming raw material of the neutral low-heat-conductivity phenolic foam material contains an acidic neutralizer alkaline salt substance, which is helpful for neutralizing an acid curing catalyst, and meanwhile, the resin with low moisture content can reduce the addition amount of the acid curing catalyst, so that the acid release amount of the phenolic foam in the use process is reduced, and the corrosion degree of the phenolic foam on a metal material is weakened; compared with the phenolic foam material only added with the inorganic filler in the prior art, the phenolic foam material has the advantages that the addition amount of the inorganic filler and the acid curing catalyst in the neutral phenolic foam material foaming raw material is small, the thermal conductivity coefficient is low, and meanwhile, the negative influence of the inorganic filler on the thermal conductivity coefficient of the phenolic foam material is overcome due to the addition of the aerogel or other substances with ultralow thermal conductivity.
Detailed Description
The following detailed description of the preferred embodiments of the present invention, taken in conjunction with the accompanying drawings, will make the advantages and features of the invention easier to understand by those skilled in the art, and will thus define the scope of the invention more clearly and clearly.
A neutral low-heat-conductivity phenolic foam material for building heat preservation is prepared from boron modified thermosetting phenolic resin, foaming agent, surfactant, acid curing catalyst, flame retardant and acid neutralizer, wherein the boron modified phenolic resin is mainly connected with benzene ring through B-O bond, the C-C bond energy is 347kJ.mol-1, and the B-O bond energy is 523 kJ.mol-1. Therefore, the boron modified phenolic resin has good heat resistance, the flame retardant can be added to improve the flame retardant and heat insulation performance, the pH value of the foam can be increased by adding the acid neutralizing agent, and the corrosion of the foam to walls and metal objects is reduced.
The flame retardant is one or more of ammonium polyphosphate, melamine cyanurate, zinc phosphate, silica aerogel, tris (1-chloro-2-propyl) phosphate and hollow glass beads.
The acid neutralizer is one or more of disodium hydrogen phosphate, potassium hydrogen tartrate, EDTA2Na, calcium propionate and calcium carbonate.
The water content of the boron modified thermosetting phenolic resin is 3-10%, and the viscosity is 3000-10000 mPa & s.
The acid curing catalyst is a mixture of acid and alcohol, wherein the acid is one or more of sulfuric acid, phosphoric acid, dimethyl benzene sulfonic acid and phenol sulfonic acid; the alcohol is one or more of ethylene glycol, diethylene glycol, glycerol and dipropylene glycol.
The foaming agent is one or more of dichloromethane, cyclopentane, n-pentane, n-hexane, n-butane, isopentane and petroleum ether.
The surfactant is one or more of polysiloxane, castor oil polyoxyethylene ether, polyoxypropylene, polytriopear ester and silane coupling agent.
Example one
The preparation method comprises the following steps of uniformly mixing 100 parts of boron modified thermosetting phenolic resin (viscosity of 7000 mPa & s, water content of 5%), 5 parts of castor oil polyoxyethylene ether, 8 parts of cyclopentane/dichloromethane (weight ratio of 5: 3), 3 parts of calcium propylene and 10 parts of dimethyl benzene sulfonic acid/sulfuric acid (weight ratio of 6: 4), spraying the materials onto a continuous aluminum foil through a mixing casting machine, entering a laminating machine for foaming and curing to form a foam product, and foaming and curing the foam material at 70 ℃ for 20 min.
Example two
Uniformly mixing boron modified thermosetting phenolic resin (with the viscosity of 7000 mPa & s and the water content of 5%), 5 parts of castor oil polyoxyethylene ether, 8 parts of cyclopentane/dichloromethane (in a weight ratio of 5: 3), 3 parts of calcium propionate, 10 parts of dimethyl benzenesulfonic acid/sulfuric acid (in a weight ratio of 6: 4) and 3 parts of silicon dioxide aerogel, spraying the mixture onto a continuous aluminum foil through a mixing and pouring machine, entering a laminating machine for foaming and curing to form a foam product, and foaming and curing the foam material at 70 ℃ for 20 min;
the difference from the first embodiment is that the addition amount of the components is as follows: adding 3 parts of silicon dioxide aerogel.
EXAMPLE III
Uniformly mixing boron modified thermosetting phenolic resin (with the viscosity of 7000 mPa & s and the water content of 5%), 5 parts of castor oil polyoxyethylene ether, 8 parts of cyclopentane/dichloromethane (in a weight ratio of 5: 3), 3 parts of calcium propionate, 15 parts of dimethyl benzenesulfonic acid/sulfuric acid (in a weight ratio of 6: 4) and 3 parts of silicon dioxide aerogel, spraying the mixture onto a continuous aluminum foil through a mixing and pouring machine, entering a laminating machine for foaming and curing to form a foam product, and foaming and curing the foam material at 70 ℃ for 20 min;
the difference from example 2 above is the amount of addition of the components: 15 parts of methylbenzenesulfonic acid/sulfuric acid (weight ratio 6: 4).
Example four
Uniformly mixing 100 parts of boron modified thermosetting phenolic resin (viscosity of 7000 mPa & s, water content of 5%), 5 parts of castor oil polyoxyethylene ether, 8 parts of cyclopentane/dichloromethane (weight ratio of 5: 3), 3 parts of calcium propionate, 10 parts of dimethyl benzenesulfonic acid/sulfuric acid (weight ratio of 6: 4) and 5 parts of silica aerogel, spraying the mixture onto a continuous aluminum foil through a mixing and pouring machine, entering a laminating machine for foaming and curing to form a foam product, and foaming and curing the foam material at 70 ℃ for 20 min;
the difference from example 2 above is the amount of addition of the components: 5 parts of silicon dioxide aerogel.
EXAMPLE five
The preparation method comprises the following steps of uniformly mixing 100 parts of boron modified thermosetting phenolic resin (viscosity of 7000 mPa & s, water content of 5%), 5 parts of castor oil polyoxyethylene ether, 8 parts of cyclopentane/dichloromethane (weight ratio of 5: 3), 5 parts of calcium propionate, 10 parts of dimethyl benzenesulfonic acid/sulfuric acid (weight ratio of 6: 4) and 5 parts of silica aerogel, spraying the mixture onto a continuous aluminum foil through a mixing and pouring machine, entering a laminating machine for foaming and curing to form a foam product, and foaming and curing the foam material at 70 ℃ for 20 min.
The difference from example 4 above is the amount of addition of the components: 5 parts of calcium propionate.
Performance testing of the neutral phenolic foam materials obtained in the examples:
1) foam density: the apparent density of the thermal insulation products in the construction sector is determined according to GB/T6343.
2) Coefficient of thermal conductivity: a foam sample having a length of 30cm, a width of 30cm and a thickness of 1 to 4.5 cm was placed between a hot plate at 35 ℃ and a cold plate at 15 ℃ of a thermal conductivity meter to measure. The thermal properties of the phenolic foam boards were determined by means of a hot plate protection device according to GB/T10294/ISO 8032: 1991.
3) pH: 5g of the phenolic foam was ground to a powder and passed through a 60 mesh sieve, placed in a 500mL Erlenmeyer flask, 250mL of distilled water was added and sealed, boiled for 1 hour and cooled at 23. + -. 2 ℃ and the pH of the aqueous solution was measured.
The results of the performance measurements obtained in the examples are shown in the following table:
from the above table data, it can be seen that: the pH value tends to increase with increasing amount of the alkaline salt calcium propionate, but the increase in amount also leads to an increase in thermal conductivity, and the thermal conductivity tends to decrease with little effect on the pH value with addition of the silica aerogel.
Although the embodiments of the present invention have been described in conjunction with the drawings, various changes or modifications may be made by the patentees within the scope of the appended claims, and they should be construed as falling within the scope of the present invention, unless they exceed the scope of the present invention described in the claims.
Claims (10)
1. The neutral low-heat-conductivity phenolic foam material for building heat insulation is characterized in that: the foaming raw materials comprise boron modified thermosetting phenolic resin, a foaming agent, a surfactant, an acid curing catalyst, a flame retardant and an acid neutralizer.
2. The neutral low thermal conductive phenolic foam material for building insulation of claim 1, wherein: the foaming raw materials comprise, by weight, 100 parts of boron modified thermosetting phenolic resin, 3-6 parts of surfactant, 5-20 parts of foaming agent, 3-6 parts of flame retardant, 5-15 parts of acid curing catalyst and 3-6 parts of acid neutralizer.
3. The neutral low thermal conductive phenolic foam material for building insulation of claim 1, wherein: the flame retardant is one or more of ammonium polyphosphate, melamine cyanurate, zinc phosphate, silica aerogel, tris (1-chloro-2-propyl) phosphate and hollow glass beads.
4. The neutral low thermal conductive phenolic foam material for building insulation of claim 1, wherein: the acid neutralizer is one or more of disodium hydrogen phosphate, potassium hydrogen tartrate, EDTA2Na, calcium propionate and calcium carbonate.
5. The neutral low thermal conductive phenolic foam material for building insulation of claim 1, wherein: the water content of the boron modified thermosetting phenolic resin is 3-10%, and the viscosity of the boron modified thermosetting phenolic resin is 3000-10000 mPa & s.
6. The neutral low thermal conductive phenolic foam material for building insulation of claim 1, wherein: the acid curing catalyst is a mixture of acid and alcohol, wherein the acid is one or more of sulfuric acid, phosphoric acid, dimethyl benzene sulfonic acid and phenol sulfonic acid; the alcohol is one or more of ethylene glycol, diethylene glycol, glycerol and dipropylene glycol.
7. The neutral low thermal conductive phenolic foam material for building insulation of claim 1, wherein: the foaming agent is one or more of dichloromethane, cyclopentane, n-pentane, n-hexane, n-butane, isopentane and petroleum ether.
8. The neutral low thermal conductive phenolic foam material for building insulation of claim 1, wherein: the surfactant is one or more of polysiloxane, castor oil polyoxyethylene ether, polyoxypropylene, polytriopear ester and silane coupling agent.
9. The preparation method of the neutral low-thermal-conductivity phenolic foam material for building insulation according to any one of claims 1 to 8, characterized by comprising the following steps: mixing the boron modified thermosetting phenolic resin, the foaming agent, the surfactant, the acid curing catalyst, the flame retardant and the acid neutralizing agent, uniformly stirring, and then foaming and curing to obtain the neutral low-thermal-conductivity phenolic foam material.
10. The preparation method of the neutral low-thermal-conductivity phenolic foam material for building thermal insulation according to claim 9, characterized by comprising the following steps: the foaming curing temperature is 60-80 ℃, and the foaming curing time is 5-30 min.
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| CN202111230300.5A CN113956608A (en) | 2021-10-22 | 2021-10-22 | Neutral low-thermal-conductivity phenolic foam material for building thermal insulation and preparation method thereof |
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| CN202111230300.5A CN113956608A (en) | 2021-10-22 | 2021-10-22 | Neutral low-thermal-conductivity phenolic foam material for building thermal insulation and preparation method thereof |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA859789A (en) * | 1970-12-29 | Pretot Monique | Phenolic resin foams | |
| CN1844233A (en) * | 2006-03-21 | 2006-10-11 | 上海胜星树脂涂料有限公司 | Method for preparing high temperature resistant phenol-formaldehyde foam composite thermal-insulating materials |
| CN101148515A (en) * | 2007-09-12 | 2008-03-26 | 北京莱恩斯涂料有限公司 | Composite pnenolic aldehyde foam heat-insulating board for building and forming method thereof |
| CN102675821A (en) * | 2012-06-08 | 2012-09-19 | 北京化工大学 | Preparation method of low-acidity phenolic foam |
| CN103613904A (en) * | 2013-11-27 | 2014-03-05 | 山东圣泉化工股份有限公司 | Low-density low-acidicity phenol formaldehyde foam board and preparation technique thereof |
| EP2708343A1 (en) * | 2012-09-18 | 2014-03-19 | Kingspan Holdings (IRL) Limited | An insulating phenolic foam |
| CN110372990A (en) * | 2019-07-17 | 2019-10-25 | 江苏中电创达建设装备科技有限公司 | A kind of Phonelic foam sandwich board preparation method and the battenboard with this method production |
-
2021
- 2021-10-22 CN CN202111230300.5A patent/CN113956608A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA859789A (en) * | 1970-12-29 | Pretot Monique | Phenolic resin foams | |
| CN1844233A (en) * | 2006-03-21 | 2006-10-11 | 上海胜星树脂涂料有限公司 | Method for preparing high temperature resistant phenol-formaldehyde foam composite thermal-insulating materials |
| CN101148515A (en) * | 2007-09-12 | 2008-03-26 | 北京莱恩斯涂料有限公司 | Composite pnenolic aldehyde foam heat-insulating board for building and forming method thereof |
| CN102675821A (en) * | 2012-06-08 | 2012-09-19 | 北京化工大学 | Preparation method of low-acidity phenolic foam |
| EP2708343A1 (en) * | 2012-09-18 | 2014-03-19 | Kingspan Holdings (IRL) Limited | An insulating phenolic foam |
| CN103613904A (en) * | 2013-11-27 | 2014-03-05 | 山东圣泉化工股份有限公司 | Low-density low-acidicity phenol formaldehyde foam board and preparation technique thereof |
| CN110372990A (en) * | 2019-07-17 | 2019-10-25 | 江苏中电创达建设装备科技有限公司 | A kind of Phonelic foam sandwich board preparation method and the battenboard with this method production |
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