CN104327449A - Phenolic foam heat-preservation material and preparation method thereof - Google Patents
Phenolic foam heat-preservation material and preparation method thereof Download PDFInfo
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- CN104327449A CN104327449A CN201410618057.8A CN201410618057A CN104327449A CN 104327449 A CN104327449 A CN 104327449A CN 201410618057 A CN201410618057 A CN 201410618057A CN 104327449 A CN104327449 A CN 104327449A
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Abstract
The invention relates to a phenolic foam heat-preservation material. The phenolic foam heat-preservation material is characterized by being mainly prepared from the following raw materials: 100 parts of phenolic resin, 2-10 parts of a phenolic resin fluidity improver, 5-15 parts of an emulsifying agent, 0.5-5 parts of a foam stabilizer, 1-10 parts of toughening and enhancing agents, 6-15 parts of a foaming agent and 6-55 parts of a reactive acid curing agent. According to the phenolic foam heat-preservation material, the phenolic resin fluidity improver is adopted so that the viscidity of a mixed system composed of the resin, the foaming agent, the emulsifying agent, the foam stabilizer, the reactive acid curing agent and the toughening and enhancing agents is reduced, materials are easy to move and the loss amount is less; polyoxyethylene grafted or blocked type aqueous methylsilicone oil is used as the foam stabilizer, so that prepared foam has fine and uniform foam holes, small heat conductivity coefficient and good heat-preservation performance; and glass fiber powder and vermiculite powder are used as the toughening and enhancing agents so that the foam flame retardant property can be improved and the production cost is reduced.
Description
Technical field
The present invention relates to a kind of preparation method of phenolic aldehyde foam thermal insulation material, belong to the category of synthesized polymer material.Phenolic aldehyde foam thermal insulation material prepared by the present invention can be used for the industry heat-insulation and heat-preservations such as building exterior wall heat preserving, ventilator trunk, petrochemical pipe, electrical equipment, instrument.
Background technology
The porous plastics such as polystyrene, polyethylene, urethane, because of features such as thermal conductivity is low, lightweight, easy constructions, are used widely in fields such as external wall heat-insulation and heat-preservation, ventilator trunk, petrochemical pipe insulations.But now widely used several porous plastics also exists the shortcomings such as easy firing, the amount of being fuming is large, toxicity is high, heat resisting temperature is low as urethane, polystyrene etc., its application in external wall, marine piping, the insulation of high temperature petrochemical pipe etc. is very limited.And phenolic foamed plastics have fire resistance good, do not burn, the advantage such as the amount of being fuming is little, fire penetration resistance is good, a kind of fire prevention of excellent performance, heat insulation, sound insulation, lightweight, energy-saving material, thermal conductivity only has 0. 018 0. 042ff/m k, heat-insulating property is better than polystyrene, urethane, polyethylene etc., the lagging material that heat insulation effect is more traditional than mineral wool, jelutong bukit, perlite, glass wool etc. is high more than 1 times, have again simultaneously the foams such as polystyrene, urethane, polyethylene far away from flame retardant property.Exist in current phenolic foamed plastics production process: (1) system viscosity is large, material transfer difficulty; (2) lower boiling alkane and hydrochloric ether is used to make whipping agent, to environmental danger; (3) foam bubble hole uneven, affect heat conductivility; (4) foams toughness, intensity are low, fall slag rate high; (5) resin originating party amount is little, foam cost height more obvious than polystyrene foam, affects its spread and uses.
Summary of the invention
The present invention is directed to the preparation method that the problems referred to above disclose a kind of phenol formaldehyde foam, the present invention adopts ethylene bis stearamide (EBS) and Tegin 55G as resol fluidity improver in phenol formaldehyde foam preparation technology, make resin, whipping agent, emulsifying agent, suds-stabilizing agent, reactive acid solidifying agent, the mixed system viscosity of toughness reinforcing, toughener composition reduces, material easily shifts, and loss amount is few; Adopt methylal Substitute For Partial lower boiling alkane and hydrochloric ether as environmentally friendly whipping agent; Polyoxyethylene grafting methyl water-based silicone oil or block type aqueous dimethylformamide silicone oil is adopted to be foam emulsion stablizer; Adopt the mixture of glass fiber powder and vermiculite power as toughness reinforcing, strengthen and fire retardant; Sulfonation polyoxyethylene nonylphenol ether, sulfonation cardanol, sulfonated castor oil and sulfocarbolic acid is adopted to be reactive acid solidifying agent.The phenol formaldehyde foam prepared by present method has that uniform foam cell, exquisiteness, intensity are high, good toughness, fall the features such as slag rate is low, reactive acid solidifying agent addition content is large, cost is low.Solve that phenol formaldehyde foam easily falls slag, matter is crisp, intensity is low, poor toughness, high in cost of production shortcoming, maintain again the traditional advantages such as low, the low cigarette of phenol formaldehyde foam thermal conductivity, superior flame retardant property.
Technical solution of the present invention is: a kind of phenolic aldehyde foam thermal insulation material, and it is prepared from primarily of following raw material:
Resol: 100 parts
Resol fluidity improver: 2-10 part
Emulsifying agent: 5-15 part
Suds-stabilizing agent: 0.5-5 part
Toughness reinforcing, toughener: 1-10 part
Whipping agent: 6-15 part
Reactive acid solidifying agent: 6-55 part.
Foregoing phenolic aldehyde foam thermal insulation material, preferred scheme is, is prepared from primarily of following raw material:
Resol: 100 parts
Resol fluidity improver: 4-8 part
Emulsifying agent: 7-12 part
Suds-stabilizing agent: 2-4 part
Toughness reinforcing, toughener: 3-8 part
Whipping agent: 8-12 part
Reactive acid solidifying agent: 12-45 part.
Foregoing phenolic aldehyde foam thermal insulation material, preferred scheme is, is prepared from primarily of following raw material:
Resol: 100 parts
Resol fluidity improver: 6 parts
Emulsifying agent: 10 parts
Suds-stabilizing agent: 3 parts
Toughness reinforcing, toughener: 6 parts
Whipping agent: 10 parts
Reactive acid solidifying agent: 20 parts.
Foregoing phenolic aldehyde foam thermal insulation material, preferred scheme is, described resol is common resole or Aromatic Polyester Polyols modified phenolic resins.
Foregoing phenolic aldehyde foam thermal insulation material, preferred scheme is, described resol fluidity improver is one in EBS, Tegin 55G or two kinds and above mixture.
Foregoing phenolic aldehyde foam thermal insulation material, preferred scheme is, described suds-stabilizing agent is polyoxyethylene grafting or block type aqueous dimethylformamide silicone oil;
Foregoing phenolic aldehyde foam thermal insulation material, preferred scheme is, described whipping agent is sherwood oil (30 ~ 60 ° of C), sherwood oil (60 ~ 90 ° of C), methylene dichloride and methylal two kinds and above mixture.
Foregoing phenolic aldehyde foam thermal insulation material, preferred scheme is, described reactive acid solidifying agent is one or two kinds and the above mixture of sulfonation polyoxyethylene nonylphenol ether, sulfonation cardanol, sulfonated castor oil and sulfocarbolic acid;
Foregoing phenolic aldehyde foam thermal insulation material, preferred scheme is, described toughness reinforcing, toughener is glass fiber powder and the vermiculite power mixture by 80:20-20:80 mass ratio.
Present invention also offers the preparation method of phenolic aldehyde foam thermal insulation material, first resol and emulsifying agent, suds-stabilizing agent, resol fluidity improver, toughness reinforcing, toughener high-speed stirring are mixed, and then it is even to add whipping agent powerful mixing, finally add reactive acid solidifying agent to mix, be transferred in the mould of preheating, put into 60-70 ° of C baking oven, be incubated foaming in 6-12 hour, slaking 24 hours, the demoulding, obtain product.
The present invention relates to a kind of preparation method of modified phenolic foam lagging material.The present invention adopts ethylene bis stearamide (EBS) and Tegin 55G as resol fluidity improver in phenol formaldehyde foam preparation technology, reduces the viscosity of phenolic foam system; Adopt methylal Substitute For Partial lower boiling alkane and hydrochloric ether as environmentally friendly whipping agent; Polyoxyethylene grafting or block type aqueous dimethylformamide silicone oil is adopted to be foam emulsion stablizer; Adopt the mixture of glass fiber powder and vermiculite power as toughness reinforcing, strengthen and fire retardant; Sulfonation polyoxyethylene nonylphenol ether, sulfonation cardanol, sulfonated castor oil and sulfocarbolic acid is adopted to be reactive acid solidifying agent.The phenol formaldehyde foam prepared by present method has uniform foam cell, exquisiteness, intensity are high, good toughness, falls the features such as slag rate is low, reactive acid solidifying agent addition content is large, cost is low.Solve that phenol formaldehyde foam easily falls slag, matter is crisp, intensity is low, poor toughness, high in cost of production shortcoming, maintain again the traditional advantages such as low, the low cigarette of phenol formaldehyde foam thermal conductivity, superior flame retardant property.
Advantage of the present invention is also embodied in:
1, adopt EBS, Tegin 55G, as internal lubricant, improves resol mobility, reduces its bulk viscosity;
2, adopt reactable acid to make solidifying agent, not only play catalysis, solidification, also become a resin body part, addition content is many simultaneously, but residual acid is few, and system acidity is little, little to materials for wall corrodibility; And cost is low, originating party amount is large;
3. methylal belongs to environmentally friendly whipping agent, as mixed foaming agent component;
4. adopt polyoxyethylene grafting or block type aqueous dimethylformamide silicone oil to be suds-stabilizing agent, the foam cell of preparation is fine and smooth evenly, thermal conductivity is little, good heat insulating;
5. adopt the mixture of glass fiber powder and vermiculite power to be toughness reinforcing, toughener and foam flame retardant properties can be improved.
Embodiment
Below by embodiment, the present invention is described in further detail.
The raw materials used Aromatic Polyester Polyols modified phenolic resins of the present invention, sulfonation polyoxyethylene nonylphenol ether and sulfonation cardanol are self-control; Other raw materials all can be bought from market.
Preparation method is as follows for Aromatic Polyester Polyols modified phenolic resins:
First prepare Aromatic Polyester Polyols
:ethylene glycol, glycol ether, Triethylene glycol, dipropylene glycol, glycerine are added reactor, warming while stirring, then under agitation adds terephthalic acid, m-phthalic acid, phthalic anhydride, then titanic acid ester is added, first control at low temperatures, reaction certain hour, then raised temperature, and held for some time, cooling vacuumizes, and maintain certain hour, cooling discharge obtains product Aromatic Polyester Polyols
;
Prepare toughening modifying resol
:reactor is added after first being dissolved by phenol, add formaldehyde solution, basic catalyst stage by stage again, regulate pH=9, add triphenylphosphate or triphenyl phosphite or triphenyl borate and make resol prepolymer at a certain temperature, add the Aromatic Polyester Polyols of above-mentioned preparation again, regulate reaction solution pH=5 with formic acid, continue to react 1h at 85 DEG C-90 DEG C, add basic solution and regulate pH=7.5, make mixture be cooled to rapidly 75 DEG C with cooling bath; Decompression dehydration 1-1.5h at 75 DEG C, viscosity controller, at 20-30mPas, obtains toughening modifying resol
.
Preparation method is as follows for sulfonation polyoxyethylene nonylphenol ether:
In reaction flask, add 100 parts of polyoxyethylene nonylphenol ethers, 20 parts of Diethylene Glycols, start stirring, temperature control 20-30 DEG C under agitation slowly (in 60-90 minute) drip 60 parts of vitriol oils; Slowly heat up after adding acid 80-85 DEG C, reacts 3 hours, be cooled to 40 DEG C, then add 10 parts of Diethylene Glycols, discharging.
Preparation method is as follows for sulfonation cardanol:
In reaction flask, add 100 parts of cardanols, temperature control 20-30 DEG C, under agitation slowly (in 60 minutes) drip 50 parts of vitriol oils, slowly heat up 85 DEG C after adding acid, react 4 hours, continue reaction 3 hours after adding acid, be cooled to 40 DEG C, add 10 parts of Diethylene Glycols again, discharging.
Normal practice of the present invention: a kind of toughen and intensify type phenolic aldehyde foam thermal insulation material, is prepared from primarily of following raw material:
Resol: 100 parts
Resol fluidity improver: 2-10 part
Emulsifying agent: 5-15 part
Suds-stabilizing agent: 0.5-5 part
Toughness reinforcing, toughener: 1-10 part
Whipping agent: 6-15 part
Reactive acid solidifying agent: 6-55 part.
The preparation method of described toughen and intensify type phenolic aldehyde foam thermal insulation material, first resol and resol fluidity improver, toughness reinforcing, toughener high-speed stirring are mixed, finally add reactive acid solidifying agent to mix, be transferred in the mould of preheating, put into 60-70 ° of C baking oven, be incubated foaming in 6-12 hour, slaking 24 hours, the demoulding, obtain product.
Described resol is common resole or Aromatic Polyester Polyols modified phenolic resins.Described resol fluidity improver is one in ethylene bis stearamide, Tegin 55G or two kinds and above mixture.Described reactive acid solidifying agent is one or two kinds and the above mixture of sulfonation polyoxyethylene nonylphenol ether, sulfonation cardanol, sulfonated castor oil and sulfocarbolic acid; Described toughness reinforcing, toughener is glass fiber powder and the vermiculite power mixture by 80:20-20:80 mass ratio.Wherein glass fiber powder specification is: particle diameter 400-800 order, water ratio <0.5%, density 2.20-2.35g/cm
3; Vermiculite power specification is: particle diameter 400-1250 order, water content <1%, thermal conductivity <0.035 W/m.K, density 2.30-2.40g/cm
3.
Embodiment 1
Successively resol and emulsifying agent, suds-stabilizing agent, Resin Flow improving agent, toughness reinforcing, toughener high-speed stirring are mixed by following formula, and then it is even to add composite foamable agent powerful mixing, finally add reactive acid solidifying agent to mix, be transferred in the mould of preheating, put into 65 ° of C baking ovens, be incubated foaming in 8 hours, slaking 24 hours, the demoulding, obtain phenolic foam products 1.
Resol: 100 parts
Resol fluidity improver: 5 parts
Emulsifying agent: 8 parts
Suds-stabilizing agent: 2 parts
Toughness reinforcing, toughener: 2 parts
Whipping agent: 10 parts
Reactive acid solidifying agent: 25 parts.
Embodiment 2
Successively resol and emulsifying agent, suds-stabilizing agent, Resin Flow improving agent, toughness reinforcing, toughener high-speed stirring are mixed by following formula, and then it is even to add composite foamable agent powerful mixing, finally add reactive acid solidifying agent to mix, be transferred in the mould of preheating, put into 70 ° of C baking ovens, be incubated foaming in 8 hours, slaking 24 hours, the demoulding, obtain phenolic foam products 2.
Aromatic Polyester Polyols modified phenolic resins: 100 parts
Resol fluidity improver: 4 parts
Emulsifying agent: 7 parts
Suds-stabilizing agent: 2 parts
Toughness reinforcing, toughener: 3 parts
Mixed foaming agent: 8 parts
Reactive acid solidifying agent: 12 parts.
Embodiment 3
Successively resol and emulsifying agent, suds-stabilizing agent, Resin Flow improving agent, toughness reinforcing, toughener high-speed stirring are mixed by following formula, and then it is even to add composite foamable agent powerful mixing, finally add reactive acid solidifying agent to mix, be transferred in the mould of preheating, put into 70 ° of C baking ovens, be incubated foaming in 6 hours, slaking 24 hours, the demoulding, obtain phenolic foam products 3.
Aromatic Polyester Polyols modified phenolic resins: 100 parts
Resol fluidity improver: 4 parts
Emulsifying agent: 7 parts
Suds-stabilizing agent: 2 parts
Toughness reinforcing, toughener: 1.5 parts
Whipping agent: 9 parts
Reactive acid solidifying agent: 35 parts.
Embodiment 4
Successively resol and emulsifying agent, suds-stabilizing agent, Resin Flow improving agent, toughness reinforcing, toughener high-speed stirring are mixed by following formula, and then it is even to add composite foamable agent powerful mixing, finally add reactive acid solidifying agent to mix, be transferred in the mould of preheating, put into 70 ° of C baking ovens, be incubated foaming in 7 hours, slaking 24 hours, the demoulding, obtain phenolic foam products 4.
Resol: 100 parts
Resol fluidity improver: 6 parts
Emulsifying agent: 10 parts
Suds-stabilizing agent: 3 parts
Toughness reinforcing, toughener: 6 parts
Whipping agent: 10 parts
Reactive acid solidifying agent: 20 parts.
Embodiment 5
Successively resol and emulsifying agent, suds-stabilizing agent, Resin Flow improving agent, toughness reinforcing, toughener high-speed stirring are mixed by following formula, and then it is even to add composite foamable agent powerful mixing, finally add reactive acid solidifying agent to mix, be transferred in the mould of preheating, put into 70 ° of C baking ovens, be incubated foaming in 7 hours, slaking 24 hours, the demoulding, obtain phenolic foam products 5.
Resol: 100 parts
Resol fluidity improver: 5 parts
Emulsifying agent: 10 parts
Suds-stabilizing agent: 3 parts
Whipping agent: 10 parts
Reactive acid solidifying agent: 25 parts.
Each embodiment gained phenol formaldehyde foam salient features is as following table:
Can find out from upper table experimental result: it is low that phenol formaldehyde foam prepared by toughness reinforcing, the toughener that add glass fiber powder and vermiculite power composition falls slag rate, and compressive strength is high, and good toughness, thermal conductivity are little, good heat insulating.
Claims (10)
1. a phenolic aldehyde foam thermal insulation material, is characterized in that, is prepared from primarily of following raw material:
Resol: 100 parts
Resol fluidity improver: 2-10 part
Emulsifying agent: 5-15 part
Suds-stabilizing agent: 0.5-5 part
Toughness reinforcing, toughener: 1-10 part
Whipping agent: 6-15 part
Reactive acid solidifying agent: 6-55 part.
2. phenolic aldehyde foam thermal insulation material according to claim 1, is characterized in that, is prepared from primarily of following raw material:
Resol: 100 parts
Resol fluidity improver: 4-8 part
Emulsifying agent: 7-12 part
Suds-stabilizing agent: 2-4 part
Toughness reinforcing, toughener: 3-8 part
Whipping agent: 8-12 part
Reactive acid solidifying agent: 12-45 part.
3. phenolic aldehyde foam thermal insulation material according to claim 1, is characterized in that, is prepared from primarily of following raw material:
Resol: 100 parts
Resol fluidity improver: 6 parts
Emulsifying agent: 10 parts
Suds-stabilizing agent: 3 parts
Toughness reinforcing, toughener: 6 parts
Whipping agent: 10 parts
Reactive acid solidifying agent: 20 parts.
4., according to the arbitrary described phenolic aldehyde foam thermal insulation material of claim 1-3, it is characterized in that, described resol is common resole or Aromatic Polyester Polyols modified phenolic resins.
5. according to the arbitrary described phenolic aldehyde foam thermal insulation material of claim 1-3, it is characterized in that, described resol fluidity improver is one in ethylene bis stearic acid amide, Tegin 55G or two kinds and above mixture.
6., according to the arbitrary described phenolic aldehyde foam thermal insulation material of claim 1-3, it is characterized in that, described suds-stabilizing agent is polyoxyethylene grafting or block type aqueous dimethylformamide silicone oil.
7., according to the arbitrary described phenolic aldehyde foam thermal insulation material of claim 1-3, it is characterized in that, described whipping agent is sherwood oil (30 ~ 60 ° of C), sherwood oil (60 ~ 90 ° of C), methylene dichloride and methylal two kinds and above mixture.
8., according to the arbitrary described phenolic aldehyde foam thermal insulation material of claim 1-3, it is characterized in that, described reactive acid solidifying agent is one or two kinds and the above mixture of sulfonation polyoxyethylene nonylphenol ether, sulfonation cardanol, sulfonated castor oil and sulfocarbolic acid.
9. according to the arbitrary described phenolic aldehyde foam thermal insulation material of claim 1-3, it is characterized in that, described toughness reinforcing, toughener is glass fiber powder and vermiculite power, and by the mixture of 80:20-20:80 mass ratio, (wherein glass fiber powder specification is: particle diameter 400-800 order, water ratio <0.5%, density 2.20-2.35g/cm
3; Vermiculite power specification is: particle diameter 400-1250 order, water content <1%, thermal conductivity <0.035 W/m.K, density 2.30-2.40g/cm
3).
10. according to the preparation method of the arbitrary described phenolic aldehyde foam thermal insulation material of claim 1-3, it is characterized in that, first resol and emulsifying agent, suds-stabilizing agent, resol fluidity improver, toughness reinforcing, toughener high-speed stirring are mixed, and then it is even to add whipping agent powerful mixing, finally add reactive acid solidifying agent to mix, be transferred in the mould of preheating, put into 60-70 ° of C baking oven, be incubated foaming in 6-12 hour, slaking 24 hours, the demoulding, obtain product.
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| CN104744886A (en) * | 2015-04-07 | 2015-07-01 | 陕西丰益瑞泽环保科技有限公司 | Enhanced foam stay-in-place building concrete template and manufacturing method thereof |
| CN105348731A (en) * | 2015-11-13 | 2016-02-24 | 安徽广源科技发展有限公司 | High-toughness plastic used for high-temperature electric appliances |
| CN106084636A (en) * | 2016-07-01 | 2016-11-09 | 南宁可煜能源科技有限公司 | A kind of novel flat-plate solar thermal collector phenolic aldehyde foam thermal insulation material |
| CN106084637A (en) * | 2016-07-01 | 2016-11-09 | 南宁可煜能源科技有限公司 | A kind of flat-plate solar collector phenol formaldehyde foam organic insulation material |
| CN106147119A (en) * | 2016-07-01 | 2016-11-23 | 南宁可煜能源科技有限公司 | A kind of flat-plate solar collector phenol formaldehyde foam inorganic heat insulation material |
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| CN107573637A (en) * | 2017-08-31 | 2018-01-12 | 苏州仲勉装饰有限公司 | A kind of preparation method of phenolic aldehyde foam thermal insulation material |
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| CN111410815A (en) * | 2020-05-18 | 2020-07-14 | 江阴市威腾铝箔合成材料有限公司 | Modified phenolic resin foam material |
| CN113831537A (en) * | 2021-09-01 | 2021-12-24 | 苏州思德新材料科技有限公司 | Preparation method of novel polyurethane foam stabilizer |
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| CN115612245A (en) * | 2022-10-14 | 2023-01-17 | 山东北理华海复合材料有限公司 | Phenolic resin thermal insulation material and preparation method thereof |
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| CN104744886A (en) * | 2015-04-07 | 2015-07-01 | 陕西丰益瑞泽环保科技有限公司 | Enhanced foam stay-in-place building concrete template and manufacturing method thereof |
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| CN105348731A (en) * | 2015-11-13 | 2016-02-24 | 安徽广源科技发展有限公司 | High-toughness plastic used for high-temperature electric appliances |
| CN106084636A (en) * | 2016-07-01 | 2016-11-09 | 南宁可煜能源科技有限公司 | A kind of novel flat-plate solar thermal collector phenolic aldehyde foam thermal insulation material |
| CN106084637A (en) * | 2016-07-01 | 2016-11-09 | 南宁可煜能源科技有限公司 | A kind of flat-plate solar collector phenol formaldehyde foam organic insulation material |
| CN106147119A (en) * | 2016-07-01 | 2016-11-23 | 南宁可煜能源科技有限公司 | A kind of flat-plate solar collector phenol formaldehyde foam inorganic heat insulation material |
| CN106433015A (en) * | 2016-09-18 | 2017-02-22 | 安徽嘉伟新材料科技有限责任公司 | Hair-reinforced phenolic foam heat-preservation sectional material and preparing method |
| CN107573637A (en) * | 2017-08-31 | 2018-01-12 | 苏州仲勉装饰有限公司 | A kind of preparation method of phenolic aldehyde foam thermal insulation material |
| CN110669193A (en) * | 2019-09-04 | 2020-01-10 | 山西晋煤集团技术研究院有限责任公司 | Environment-friendly harmless high-flame-retardant polymer material for coal mine water plugging and coal rock reinforcing and preparation method thereof |
| CN110669193B (en) * | 2019-09-04 | 2021-07-06 | 山西晋煤集团技术研究院有限责任公司 | Environment-friendly harmless high-flame-retardant polymer material for coal mine water plugging and coal rock reinforcing and preparation method thereof |
| CN111410815A (en) * | 2020-05-18 | 2020-07-14 | 江阴市威腾铝箔合成材料有限公司 | Modified phenolic resin foam material |
| CN113831537A (en) * | 2021-09-01 | 2021-12-24 | 苏州思德新材料科技有限公司 | Preparation method of novel polyurethane foam stabilizer |
| CN115109382A (en) * | 2022-08-05 | 2022-09-27 | 福建天利高新材料有限公司 | Rare earth reinforced phenolic aldehyde fireproof foam board |
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| CN115612245A (en) * | 2022-10-14 | 2023-01-17 | 山东北理华海复合材料有限公司 | Phenolic resin thermal insulation material and preparation method thereof |
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Application publication date: 20150204 |