CN103435970A - Modified phenolic foam for heat preservation of wall body and preparation method thereof - Google Patents

Modified phenolic foam for heat preservation of wall body and preparation method thereof Download PDF

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Publication number
CN103435970A
CN103435970A CN2013103851881A CN201310385188A CN103435970A CN 103435970 A CN103435970 A CN 103435970A CN 2013103851881 A CN2013103851881 A CN 2013103851881A CN 201310385188 A CN201310385188 A CN 201310385188A CN 103435970 A CN103435970 A CN 103435970A
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phenolic foam
modified phenolic
foam
oil
parts
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CN103435970B (en
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刁桂芝
刘振贤
刘光华
王继梅
王志新
李清海
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China Building Materials Academy CBMA
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Abstract

The invention relates to modified phenolic foam for heat preservation of a wall body and a preparation method thereof. The modified phenolic foam comprises the following raw materials in parts by weight: 100 parts of phenolic resin, 0.1-18 parts of inorganic modifying agents, 3-7 parts of coupling agents, 3-15 parts of organic modifying agents, 6-18 parts of foaming agents and 6-20 parts of solidifying agents. According to the invention, the phenolic resin can react with a polyhydroxy modified compound and can be effectively combined with an inorganic material through a grafting functional group interspersed compound process, so that the structure and property of a phenolic foam heat-preserving material are changed, and the phenolic resin has the advantages of expandability, viscosity, high strength, high and low temperature resistance and good heat-preserving fire-proof property. Compared with the traditional phenolic foam, the modified phenolic foam disclosed by the invention is greatly enhanced in flexibility, mechanical strength and fire-proof flame-retardant property.

Description

A kind of modified phenolic foam for wall thermal insulating and preparation method thereof
Technical field
The invention belongs to the construction wall field of heat insulating materials, relate to a kind of compound insulating material of the modified phenolic for wall thermal insulating and preparation method thereof, particularly relate to a kind of modified phenolic foam for wall thermal insulating and preparation method thereof.
Background technology
At present, approximately 80% building thermal insulation material is organic combustible matl, make a general survey of market, existing organic insulation material is difficult to reach the requirement of country to fire resistance, and inorganic materials because water-intake rate is large, easily " dewfall ", do not reach the requirement of heat preservation energy-saving, therefore, along with progressively promulgation and the enforcement of national policy, the product that research and development have insulation and fire-proof function concurrently is the irreversible development trend in following external wall outer insulation market.Can play fire prevention and " double insurance " effect be incubated with inorganic material-modified organic insulation material.Phenolic aldehyde foam thermal insulation material relies on and adds the material that fire retardant obtains that the different of essence are arranged from common macromolecule resin, phenolic foam board fire prevention, chance naked light do not burn, flame resistant penetrates, do not melt, can not distribute toxic smog yet, without drippage, and there are light weight, corrosion-free, insulation, energy-conservation, sound insulation, the characteristics that inexpensive, the use temperature scope is wide, be heat insulating energy saving material preferably.
On market, existing phenolic foam board exists easy efflorescence, fragility is large and physical strength is low problem, can in the phenol formaldehyde foam production process, add organic and inorganic modified dose, improve the easy efflorescence defect of phenol formaldehyde foam, increase material snappiness, improve its ultimate compression strength, cohesive strength and combustionproperty.The patent documentation of relevant phenolic foam material and preparation method thereof is more, wherein, in the patent documentation that publication number is CN1428372A, only used organic modifiers terminal hydroxyl polybutadiene liquid rubber, furfural, polyethers, amidogen ether etc. to carry out modification to phenol formaldehyde foam, improved compressive strength and flexural strength performance, but thermal conductivity is higher; Having put down in writing a kind of preparation method of modified phenolic foam in the patent documentation that publication number is CN1065077A, is to adopt HO-CH 2-R, HO-CH 2-R-CH 2-HO and urea, benzene mixed cresols, phynol residues, dihydroxyphenyl propane residue and perlite powder, pumice sand, pure aluminium silicate and phosphorylation flue dust carry out modification to phenol formaldehyde foam, it adopts organic and inorganic modified dose can only the limited raising strength of materials, the shortcoming of phenol formaldehyde foam dry linting do not have be improved significantly, limited the application of phenolic foam material in high-end market; In the patent documentation that publication number is CN1609128A, adopt urea, aluminium hydroxide, pearlstone, wilkinite, talcum powder as properties-correcting agent, improved combustionproperty, but water absorption decreased is not obvious.
Summary of the invention
The modified phenolic foam that the purpose of this invention is to provide a kind of cheap, excellent performance for wall thermal insulating.
Modified phenolic foam for wall thermal insulating provided by the present invention, its raw material comprises the component of following ratio of weight and number: 100 parts of resol, inorganic modified dose of 0.1-18 part, 3-7 part coupling agent, 3-15 part organic modifiers, 6-18 part whipping agent, 6-20 part solidifying agent.
Described resol can be thermoset soluble phenolic resin, i.e. resole.
Described inorganic modified dose is xonotlite powder, glass bead powder, mullite powder or light calcium carbonate powder.
Described coupling agent is dibutyl phthalate, KH550(silane coupling agent), the KH560(silane coupling agent) or Tritolyl Phosphate etc.
Described organic modifiers is polyethylene or vegetables oil (peanut oil, sweet oil or Oleum Gossypii semen), or the mixed vegetable oil formed in any proportion by two or more vegetables oil, or polyethylene and vegetables oil (peanut oil, sweet oil or Oleum Gossypii semen) mixing in any proportion, or the mixing in any proportion of polyethylene and mixed vegetable oil (two or more in peanut oil, sweet oil and Oleum Gossypii semen form in any proportion).
Described whipping agent is the naphthenic whipping agent, specifically can be pentamethylene etc.
Described solidifying agent is the mixing acid that one or more acid in sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, tosic acid and acetic acid form.
The density of this modified phenolic bubble is 30-80kg/m 3.
The present invention also provides a kind of method for preparing above-mentioned modified phenolic foam, in adding resol by inorganic modified dose under agitation condition, then add coupling agent, organic modifiers, whipping agent and solidifying agent, stir, be poured on the sheet material tinuous production and keep 2-12 hour under temperature 18-90 ℃, make between component to occur successively to obtain modified phenolic foam after crosslinked, foaming, curing reaction.
Concrete, each raw material quantitatively is transported to the pouring foaming machine with volume pump, after raw material carries out high-speed mixing in mixing head, by mixing head scanning cast, back and forth inject and be furnished with automatic transmission tourelle from top, and have in the die cavity of controlling up and down on the high-low plate conveying belt, produce continuously.
Wall thermal insulating provided by the invention is compared with traditional phenol formaldehyde foam with modified phenolic foam, and snappiness, physical strength and fire retardant performance are largely increased.Modified phenolic foam of the present invention is to adopt organic materials modification, the interspersed recombining process method of inorganic materials, and adds other additive to make in synthetic.On the one hand, the present invention adds preferred organic modifiers in resol, firmly crisp to change phenol formaldehyde foam, yielding, easily efflorescence, fall the defects such as slag and physical strength are low, on the other hand by with inorganic materials xonotlite powder, mullite powder, glass bead powder or light calcium carbonate powder etc. are compound, inorganic materials can " be interted compound " with the resol network, to improve the intensity of phenolic foams, binding property, high and low temperature resistance, flame retardant properties etc., and can with the effective combination of inorganic materials, thereby change structure and the performance of phenolic aldehyde foam thermal insulation material, make resol there is expandability, cohesiveness, high epistasis, resistant of high or low temperature and good insulated fire performance, with traditional phenol formaldehyde foam, compare, snappiness, physical strength and fire retardant performance are largely increased.
Modified phenolic foam of the present invention has the following advantages:
L, thermotolerance: product does not burn under 1000 ℃ of flame sprayings, and smokeless, without obnoxious flavour, distributes, and without the pyrolytic decomposition drippage, reaches the difficult combustion of domestic GB8625-1997 B1 level.
2, product density: product density is little, lightweight, the broad (50-60kg/m of density range 3), can be selected according to use occasion, ultimate compression strength is greater than 120kpa.
3, nontoxic smokeless: as to only have hydrogen, carbon and Sauerstoffatom in the phenolic aldehyde molecule, when pyrolytic decomposition, can only produce the product that hydrogen, carbon and oxygen form, except a small amount of CO, without any other toxic gas.The maximum smoke density of phenol formaldehyde foam is less than 5.0%, and it is quite low with the maximum smoke density 74% of high-density phenol formaldehyde foam, comparing.
4, anti-flame penetrates: phenol formaldehyde foam under the flame direct effect, have coking, without dropping, without curling, without melting phenomenon; after flame; foams retain substantially; only have surface to form one deck " graphite foam " layer; effectively protected the foamy structure in the layer, more than its anti-Flame resistance time can reach 1h.
5, thermal insulation: phenol formaldehyde foam has evenly fine unicellular structure, and thermal conductivity is low, 0.030-0.035W/ (m.k) only, and its heat-insulating property and polyurethane foam are suitable, are better than polystyrene foam.
6, the use temperature scope is wide: the intensity temperature influence of phenol formaldehyde foam is not obvious, under low temperature (even-2000 ℃), shrinkage, cold short does not occur, its physical strength is substantially constant, in the situation that 150 ℃ continuous stressed, can keep 90% of room temperature strength, it can be at-196-150 ℃ scope life-time service.
7, corrosion resistant is anti-aging: outside decapacitation is corroded by highly basic, phenol formaldehyde foam is the erosion of all mineral acid, organic acid, organic solvent and the salt of ability almost.Long-term exposure in the sun, without obvious catabiosis, is compared longer service life with other thermal insulation material.
8, water protection against the tide: phenol formaldehyde foam has good unicellular structure, and water-intake rate low (7%) water vapor penetrating power is strong, not there will be dewfall when cold insulation.
9, current, domestic phenol formaldehyde foam low-temp foaming method is all hand-manipulated and can only batch production.The invention provides and be applicable to formula and the technique that the mechanical foaming machine is produced, adopt mechanical foaming machine foam production, but but but also continous way cast-in-site also of intermittent type, this mode of production and means make mass industrialized production become possibility, and have better quality with the mode of production hand-manipulated than foam.
Below in conjunction with specific embodiment, the present invention is described in further details.
The accompanying drawing explanation
The scanning electron microscope comparison diagram (* 40 times) that Fig. 1 is two kinds of (modification, unmodified) phenolic foam materials
Embodiment
The contriver realizes in the research to phenolic foam material, the organic and inorganic modified defect of improving the easy efflorescence of phenol formaldehyde foam that is of value to, increase material snappiness, improve its ultimate compression strength, cohesive strength and combustionproperty.So which kind of key is to use material modified and how to mate.
According to documents and materials, can improve the flexible organic modifiers of phenolic foam material can be trimeric cyanamide, urea, alcohols, mineral oil, polyvinyl acetate, acrylate, polymeric polyisocyanate, base polyurethane prepolymer for use as, furfuryl alcohol polymer, polyester, rubber, xylogen etc., the present invention considers and the coordinating of inorganic modified dose and other raw material, preferably polyethylene and vegetables oil carry out modification to phenol formaldehyde foam, experimental results show that, polyethylene and vegetables oil not only can improve the snappiness of phenolic foam material, can also improve the intensity of material.
Equally, for the inorganic materials of phenol formaldehyde foam modification of the present invention, also need to consider and the coordinating of other raw material, the present invention proposes inorganic modified dose of suitable needs and possesses following performance:
A. there is the light thermal-insulation performance: add inorganic materials can increase unit weight and the thermal conductivity of phenol formaldehyde foam, affect the heat insulation effect of phenol formaldehyde foam, therefore select the inorganic materials with light thermal-insulation performance, can, in modification, inorganic materials be reduced to minimum to the impact of phenol formaldehyde foam heat insulation effect.
B. fire retardant performance: adding very important effect of inorganic materials is exactly the fire retardant performance that improves phenol formaldehyde foam, therefore, select the inorganic materials with fire retardant performance can under limited volume, improve as far as possible the fire retardant performance of phenol formaldehyde foam.
C. with resol, good consistency is arranged: can with the resol network, " intert compound ", play good reinforced effects.
D. cheap, can reduce the cost of phenolic foam material.
Therefore, be suitable for inorganic modified dose of the present invention and can be xonotlite powder, glass bead powder, mullite powder or light calcium carbonate powder etc.
Based on this, the modified phenolic foam for wall thermal insulating that the present invention proposes, its raw materials by weight portion ratio comprises: 100 parts of resol, 0.1-18 inorganic modified dose of part, 1-10 part coupling agent, 3-15 part organic modifiers, 2-18 part whipping agent, 6-20 part solidifying agent.
Wherein resol is thermoset soluble phenolic resin, i.e. resole.
The structural formula of resol used is:
The present invention can use commercially available molecular weight at 300-700, and range of viscosities is at the heat-reactive phenolic resin of 150~2000mPaS.Resol is the main body core material of phenol formaldehyde foam, forms the agent structure of foam materials after sclerosis.
Inorganic modified dose (mineral filler) can be xonotlite powder, glass bead powder, mullite powder or light calcium carbonate powder etc.
Coupling agent can be dibutyl phthalate, KH550(silane coupling agent), the KH560(silane coupling agent), Tritolyl Phosphate.The effect of coupling agent is for coupling resol and mineral filler, strengthens its cohesiveness, improves the machinery of product, the performance such as water-fast, anti-aging.Coupling agent is applied in the resol of inorganic modified dose of filling, can increase substantially the physical and mechanical property such as dry hygrometric state bending strength, ultimate compression strength, shearing resistance of strongthener, and improve wettability and the dispersiveness of filler (referring to inorganic modified dose) in resol.
Organic modifiers is polyethylene or vegetables oil (peanut oil, sweet oil or Oleum Gossypii semen) or the mixed vegetable oil that is comprised of two or more vegetables oil, described organic modifiers also can be the mixture of above-mentioned two or more organic modifiers, in a formula, can add respectively polyethylene and vegetables oil (peanut oil, sweet oil or Oleum Gossypii semen), polyethylene and mixed vegetable oil (two or more in peanut oil, sweet oil and Oleum Gossypii semen form) as organic modifiers, the effect of organic modifiers is the toughness that increases phenolic foam material.
Whipping agent can be the naphthenic whipping agent, specifically can be pentamethylene, azoformamide, benzol sulfohydrazide sodium bicarbonate etc.The effect of whipping agent is to make mixing raw material expanded foamed.
Solidifying agent can be the mixing acid of one or more the acid compositions in sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, acetic acid, tosic acid etc.The effect of solidifying agent is to accelerate Foaming of phenolic resin to solidify.
The present invention also provides a kind of method for preparing above-mentioned modified phenolic foam, in adding resol by inorganic modified dose under agitation condition, then add coupling agent, organic modifiers, whipping agent and solidifying agent, stir, be poured on the sheet material tinuous production and keep 2-12 hour under temperature 18-95 ℃, make between component reaction jointly, after crosslinked, foaming, curing reaction occur successively, obtain modified phenolic foam.
Described crosslinked refer in particular in the present invention between the resol molecule or resol and organically-modified agent molecule between mutually bonding cross-linking become the stable bodily form molecule of network structure, this reaction makes the macromole of line style or slight branched chain type be transformed into tridimensional network.Described foaming refers to that whipping agent makes raw material expand, and forms even vesicular structure.Described solidify refers to that raw material forms stable build superpolymer under the effect of solidifying agent, has advantages of that good heat resistance, dimensional stability are high.
In addition, can control the density of phenol formaldehyde foam by the inorganic modified dose of incorporation with whipping agent, make the density of phenol formaldehyde foam should reach 30-80kg/m 3.Within the specific limits, increase along with inorganic modified dose of volume, the density of phenol formaldehyde foam increases, the density of phenolic foam material reduces with the increase of the volume of whipping agent, can control the density of phenol formaldehyde foam by the inorganic modified dose of coupling with the incorporation of whipping agent, adapt to the actual needs that use.
Embodiment is implemented take technical solution of the present invention under prerequisite, has provided detailed embodiment and concrete operating process, and embodiment will contribute to understand the present invention, but protection scope of the present invention is not limited to following embodiment.
In following embodiment, method therefor is ordinary method if no special instructions.
Embodiment, prepare modified phenolic foam
Composition of raw materials and the preparation technology parameter of the modified phenolic foam of embodiment 1-6 and comparative example 1-3 are as shown in table 1:
The composition of raw materials of the modified phenolic foam of table 1 embodiment 1-6 and comparative example and preparation technology parameter (unit: weight part can be kg)
The solvable heat-reactive phenolic resin adopted in embodiment is resole, and by Langfang, benefit group energy-saving material company limited produces (range of viscosities is at 150~2000mPaS).Other raw material also is and is purchased.
Prepare phenol formaldehyde foam by formula and processing parameter shown in table 1, by inorganic modified dose, under agitation condition, add resol, then add coupling agent, organic modifiers, whipping agent, solidifying agent, stir, be poured into the sheet material tinuous production.Specifically each raw material quantitatively is transported to the pouring foaming machine with volume pump, after raw material carries out high-speed mixing in mixing head, by mixing head scanning cast, from top, back and forth inject and be furnished with automatic transmission tourelle, and have in the die cavity of controlling up and down on the high-low plate conveying belt, produce continuously.Keep 2-12 hour under temperature 18-90 ℃, reaction jointly between component, after crosslinked, foaming occurs successively, solidifying, obtain modified phenolic foam.
The abscess result of test 1, modified phenolic foam material detects
Heat retaining property, the water-absorbent of foam structure to foam, mechanical property has important impact.Respectively to embodiment 1-6(modified phenolic resins) and the unmodified resol of comparative example 1-3() phenolic foam material for preparing carries out performance test.Test result, in Table 3, can find out, unmodified phenol formaldehyde foam various aspects of performance index prepared than comparative example 1-3 by modified phenolic foam prepared by embodiment of the present invention 1-6 all has clear improvement.Fig. 1 is two kinds of (the unmodified phenol formaldehyde foam hole shape of A-looks, B-modified phenolic foam hole shape looks) the scanning electron microscope comparison diagram (* 40 times) of phenolic foam material, can find out, heat-resistant, high strength modified phenolic foam abscess of the present invention is even, and pore structure is complete, tight, and between thin-film barrier is arranged, overwhelming majority abscess is unicellular structure, and unmodified phenol formaldehyde foam abscess integrity is poor, fragmentation is many, and rate of closed hole is low.
The Performance Detection of test 2, modified phenolic foam
The performance of the phenolic foam material according to the method for standard GB/T20974 and GB8624 regulation prepared by embodiment 1-6 and comparative example 1-3 is detected, and wherein, the standard performance index of phenol formaldehyde foam is as shown in table 2:
The standard performance index of table 2 phenol formaldehyde foam
Detected result is as shown in table 3.
The performance test results of the modified phenolic foam of table 3 embodiment 1-6 and comparative example
Table 3 data show: the equal conformance with standard of the performance index of modified phenolic foam prepared by embodiment of the present invention 1-6, and the index that obviously is better than comparative example 1-3, the phenol formaldehyde foam that embodiment 1-6 prepares all there is higher compression and cohesive strength, show that the snappiness of material has obtained remarkable improvement.There is higher oxygen index and lower thermal conductivity, the combustionproperty of illustrative material and good heat insulating.Embodiment 1 has low density but intensity is higher and snappiness is good, and thermal conductivity is low, so good heat insulating.Embodiment 2 and embodiment 3 there is excellent intensity and oxygen index high, so fire resistance and good mechanical property, embodiment 4 density are higher, but have extraordinary ultimate compression strength and excellent resistance to flame energy.Embodiment 5 and embodiment 6 have excellent over-all properties.Show that but phenol formaldehyde foam of the present invention has possessed good viscosity, snappiness, high epistasis, resistant of high or low temperature and good insulated fire performance.
Unmodified phenol formaldehyde foam prepared with comparative example 1-3 by modified phenolic foam prepared by embodiment of the present invention 1-6 is compared, and intensity and combustionproperty all are improved.
In addition, compared under physical environment the phenolic foam material of placing 6 months, by the present invention's phenol formaldehyde foam of producing of filling a prescription, do not had the dry linting situation to occur, fallen the slag performance and be better than common phenol formaldehyde foam and other modified phenolic foam material.

Claims (10)

1. the modified phenolic foam for wall thermal insulating, comprise following raw material (by weight): 100 parts of resol, inorganic modified dose of 0.1-18 part, 3-7 part coupling agent, 3-15 part organic modifiers, 6-18 part whipping agent, 6-20 part solidifying agent.
2. modified phenolic foam according to claim 1, it is characterized in that: described resol can be thermoset soluble phenolic resin, i.e. resole.
3. modified phenolic foam according to claim 1 and 2 is characterized in that: described inorganic modified dose is xonotlite powder, glass bead powder, mullite powder or light calcium carbonate powder.
4. according to the described modified phenolic foam of claim 1-3 any one, it is characterized in that: described coupling agent is dibutyl phthalate, KH550(silane coupling agent), the KH560(silane coupling agent) or Tritolyl Phosphate etc.
5. according to the described modified phenolic foam of claim 1-4 any one, it is characterized in that: described organic modifiers is polyethylene or vegetables oil (peanut oil, sweet oil or Oleum Gossypii semen), or the mixed vegetable oil formed in any proportion by two or more vegetables oil, or polyethylene and vegetables oil (peanut oil, sweet oil or Oleum Gossypii semen) mixing in any proportion, or the mixing in any proportion of polyethylene and mixed vegetable oil (two or more in peanut oil, sweet oil and Oleum Gossypii semen form in any proportion).
6. according to the described modified phenolic foam of claim 1-5 any one, it is characterized in that: described whipping agent is the naphthenic whipping agent, specifically can be pentamethylene etc.
7. according to the described modified phenolic foam of claim 1-6 any one, it is characterized in that: described solidifying agent is the mixing acid that one or more acid in sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, tosic acid and acetic acid form.
8. according to the arbitrary described modified phenolic foam of claim 1-7, it is characterized in that: the density of phenol formaldehyde foam is 30-80kg/m 3.
9. a method for preparing the described modified phenolic foam of claim 1-8 any one, in adding resol by inorganic modified dose under agitation condition, then add coupling agent, organic modifiers, whipping agent and solidifying agent, stir, be poured on the sheet material tinuous production and keep 2-12 hour under temperature 18-90 ℃, make between component to occur successively to obtain modified phenolic foam after crosslinked, foaming, curing reaction.
10. method according to claim 9, it is characterized in that, each raw material quantitatively is transported to the pouring foaming machine with volume pump, after raw material carries out high-speed mixing in mixing head, by mixing head scanning cast, back and forth inject and be furnished with automatic transmission tourelle from top, and have in the die cavity of controlling up and down on the high-low plate conveying belt, produce continuously.
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CN104403261A (en) * 2014-09-04 2015-03-11 中国建筑材料科学研究总院 Inorganic material-modified phenolic foam insulation material with low water absorption and preparation method thereof
WO2015194174A1 (en) * 2014-06-18 2015-12-23 旭化成建材株式会社 Phenol resin foam and method for manufacturing same
CN104151772B (en) * 2014-08-22 2016-08-24 太原理工大学 A kind of preparation method of fibre reinforced phenolic insulation material
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
CN106589796A (en) * 2016-12-22 2017-04-26 河北建筑工程学院 Pumice phenolic resin compound foam material and preparation method thereof
CN106589792A (en) * 2016-12-22 2017-04-26 河北建筑工程学院 Composite phenolic foam insulation material and preparation method thereof
CN106751723A (en) * 2016-12-14 2017-05-31 上海电力学院 A kind of insulation material for solar thermal collection system and preparation method thereof
CN111075103A (en) * 2019-12-10 2020-04-28 北京中建建筑设计院有限公司 Assembled building heat-insulation external wall panel and manufacturing method thereof
CN113427681A (en) * 2021-07-26 2021-09-24 江苏美龙新材料有限公司 Manufacturing method of full-core reinforced composite template

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CN103232680A (en) * 2013-04-27 2013-08-07 苏州市德莱尔建材科技有限公司 Imitation wood phenolic plastic building material and preparation method thereof
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CN104151772B (en) * 2014-08-22 2016-08-24 太原理工大学 A kind of preparation method of fibre reinforced phenolic insulation material
CN104403261A (en) * 2014-09-04 2015-03-11 中国建筑材料科学研究总院 Inorganic material-modified phenolic foam insulation material with low water absorption and preparation method thereof
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
CN106751723A (en) * 2016-12-14 2017-05-31 上海电力学院 A kind of insulation material for solar thermal collection system and preparation method thereof
CN106589796A (en) * 2016-12-22 2017-04-26 河北建筑工程学院 Pumice phenolic resin compound foam material and preparation method thereof
CN106589792A (en) * 2016-12-22 2017-04-26 河北建筑工程学院 Composite phenolic foam insulation material and preparation method thereof
CN106589792B (en) * 2016-12-22 2019-10-29 河北建筑工程学院 A kind of composite phenol formaldehyde cellular insulant and preparation method thereof
CN111075103A (en) * 2019-12-10 2020-04-28 北京中建建筑设计院有限公司 Assembled building heat-insulation external wall panel and manufacturing method thereof
CN113427681A (en) * 2021-07-26 2021-09-24 江苏美龙新材料有限公司 Manufacturing method of full-core reinforced composite template

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