CN103866871A - Method for manufacturing composite phenolic foam insulation board covered with sand - Google Patents
Method for manufacturing composite phenolic foam insulation board covered with sand Download PDFInfo
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- CN103866871A CN103866871A CN201410119544.XA CN201410119544A CN103866871A CN 103866871 A CN103866871 A CN 103866871A CN 201410119544 A CN201410119544 A CN 201410119544A CN 103866871 A CN103866871 A CN 103866871A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A30/00—Adapting or protecting infrastructure or their operation
- Y02A30/24—Structural elements or technologies for improving thermal insulation
- Y02A30/242—Slab shaped vacuum insulation
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B80/00—Architectural or constructional elements improving the thermal performance of buildings
- Y02B80/10—Insulation, e.g. vacuum or aerogel insulation
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Abstract
The invention relates to a method for manufacturing a composite phenolic foam insulation board covered with sand. The method includes the steps that after phenolic resin adhesion agents are sprayed on lining cloth in advance, sand is implanted through a gravity method, then the lining cloth is formed after heating and primary curing are carried out, the non-sand-implanted face of the bottom lining is coated with phenolic foam feed liquid and then heated, foaming curing is carried out, a phenolic foam layer is formed, meanwhile, post curing of the phenolic resin adhesion agents and integrated adhesion of the bottom lining and the foam layer are achieved, and demolding is carried out after cooling. In addition, a composite phenolic foam insulation board with two faces covered with sand can also be manufactured. According to the method, construction of thermal insulation is achieved and meanwhile wall decoration is completed.
Description
Technical field
The present invention relates to building thermal insulation material, be specifically related to a kind of preparation method with sand clad can composite phenol formaldehyde foam composite insulation board.
Background technology
Traditional phenolic foam heat insulation plate used for building exterior wall is being installed after wall, need to apply cement mortar and carry out incrustation at the external surface of warming plate.This construction method complex process, site operation workload is large, long in time limit, efficiency is low, and construction quality is subject to job site condition and constructor's artificial factors, and wall insulation system construction quality easily fluctuates.In recent years, there is the composite phenol formaldehyde foam heat-insulating board of surperficial coating cement mortar or other inorganic coatings, simplified wall thermal insulating work progress.
WO2002038879A1 (2002) and CN1586849A(2005) disclose the composite insulation boards that applies cement mortar on phenolic foam board surface.DE202011001989 (2011) discloses the method that then applies cement mortar at warming plate surface bonding glass fiber.CN202577625U (2012) utility model discloses a kind of composite insulation boards of inorganic material coating organic material, by perfusion or bonding mode by compound to inorganic material insulation layer and organic material central layer.CN102515641A (2012) discloses fire-retardant cement-based interface mat for a kind of exterior-wall heat insulation, and its preparation technology is: quartz powder, solid flame retardant, cement mixing is even, make inorganic powder; Emulsion polymerization, deionized water, defoamer, bactericide are mixed, make polymer agent material; Inorganic powder and polymer agent material are uniformly mixed, make fire-retardant cement-based interface slurry, then cement-based interface slurry is applied to glass fibre belt surface, fire-retardant cement-based interface mat for exterior-wall heat insulation is made in oven dry, be used for being compounded in the organic insulation material surfaces such as hard-foam polyurethane, phenolic aldehyde, XPS, improve the anti-flammability on warming plate surface.CN203022145U(2012) utility model provides a kind of phenolic foam heat insulation plate of composite flame-proof material, this warming plate is to apply one deck fire proofing apply one deck interfacial agents on phenolic foam heat insulation plate external surface after again, strengthen the surface strength of plate body, improved the fire retardant performance of plate body.CN102704586A(2012) disclose a kind of modified phenolic composite insulation boards, comprised modified phenolic warming plate, interfacial agents layer and quartz sand layer, the upper and lower faces of modified phenolic warming plate is respectively equipped with interfacial agents layer, and interfacial agents layer is provided with quartz sand layer; In the two-sided interfacial agents of smearing of modified phenolic warming plate, then two-sided compound quartz sand, last baking and curing.CN203347037U (2013) utility model discloses a kind of external wall insulation for building, this warming plate comprises phenol formaldehyde foam core layer and the cement-based coiled material layer that is positioned at phenol formaldehyde foam core layer one or both sides, and cement-based coiled material layer is fixedly connected with phenol formaldehyde foam core layer.The composite phenol formaldehyde foam heat-insulating board of these patent reports, simplified the work progress of phenol formaldehyde foam exterior wall heat-preserving system, and finish coat can carry out batch production design customization, the construction quality of effective guarantee wall insulation system.But, according to existing composite phenol formaldehyde foam thermal insulation board fabrication method, screed and architectural surface are all to carry out follow-up Compound Machining after acquisition phenol formaldehyde foam sheet material finished product, first obtain phenol formaldehyde foam sheet material, then apply mortar or decorative layer be adhered to plate surface with adhesive at plate surface.This division system making method complex process, occupation of land is many, and production efficiency is low, and workman's manipulation strength is large, is unfavorable for the practical application of composite phenol formaldehyde foam heat-insulating board.
Need at present the composite phenol formaldehyde foam heat-insulating board manufacture method that a kind of cost is low, production efficiency is high badly, the method should be able to obtain by easy technique the pnenolic aldehyde foam heat-insulating board of the sand clad can of excellent performance.
Summary of the invention
In order to solve problems of the prior art, the inventor has carried out research with keen determination, found that: pre-spraying after aerodux on lining cloth, lining cloth uppper sand embedding by gravitational method at pre-spraying aerodux, then after heating primary solidification, make end liner, the non-sand face of planting at end liner applies phenol formaldehyde foam feed liquid, then heating is carried out foamed solidification and is formed phenol formaldehyde foam layer, realize the rear of phenol aldehyde adhesive solidifies and end liner and froth bed integrated bonding simultaneously, the cooling rear demoulding, can obtain sand clad can composite phenol formaldehyde foam heat-insulating board, thereby complete the present invention.
The preparation method who the object of the present invention is to provide a kind of sand clad can composite phenol formaldehyde foam heat-insulating board, the method comprises the following steps:
(1) pre-spraying aerodux on lining cloth, then form surperficial sand grains layer by gravitational method at the lining cloth uppper sand embedding of pre-spraying aerodux, the lining cloth that forms surperficial sand grains layer is heated and within 5～60 minutes, makes, after aerodux primary solidification, to make end liner at 90～130 ℃;
(2) end liner good primary solidification is faced down to plant sand, the non-supine mode of sand of planting is laid on mould, apply phenol formaldehyde foam feed liquid at the non-sand face of planting, then at 45～90 ℃, heating makes phenol formaldehyde foam feed liquid foamed solidification form phenol formaldehyde foam layer, and the aerodux in foamed solidification in end liner further solidifies after crosslinked carrying out;
(3) form after phenol formaldehyde foam layer at phenol formaldehyde foam feed liquid foamed solidification, cooling die is to room temperature, and the then demoulding, can obtain described sand clad can composite phenol formaldehyde foam heat-insulating board;
Wherein, described aerodux is to mix preparation by the composition that comprises following weight proportion:
100 parts, foamable phenolic resins,
2～6 parts of polyethylene glycol oxides,
Wherein, described phenol formaldehyde foam feed liquid is to mix preparation by the composition that comprises following weight proportion:
Wherein, described surfactant is to be selected from one or more in Tween-40, Tween-80, AK8812, L5440 and polyethylene glycol oxide; Described blowing agent is one or more in benzinum, pentane, pentamethylene, n-hexane and carrene; Described nertralizer is one or more in barium hydroxide, aluminium hydroxide, magnesium hydroxide, magnesia and the calcium oxide of solid granular; Described carbon black is one or more in N220, N234, N326, N330, N339, N375; Described curing compound be inorganic acid as sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, and organic acid is as one or more in formic acid, oxalic acid, p-methyl benzenesulfonic acid, xylene monosulfonic acid, pyrovinic acid and DBSA.
In the preparation of phenol formaldehyde foam feed liquid, the mixture of the preferred p-methyl benzenesulfonic acid of described curing compound or p-methyl benzenesulfonic acid and sulfuric acid.
In the preparation of phenol formaldehyde foam feed liquid, described surfactant is 3～4 weight portions preferably, and blowing agent is 5～8 weight portions preferably, and nertralizer is 10～20 weight portions preferably.
In a kind of preparation method of sand clad can composite phenol formaldehyde foam heat-insulating board, after end liner is laid on mould, be preheated to after 30～40 ℃, apply fast phenol formaldehyde foam feed liquid at the non-sand face of planting of end liner, then put into the baking oven foamed solidification of 60～80 ℃.
In the present invention, described lining cloth is one or more in nonwoven, glass fabric, textile sheet, sand grains be a kind of in river sand, extra large sand, ore in sand form, artificially colored color sand or how in.
In the present invention, described foamable phenolic resins is by comprising the following steps preparation:
(a) phenol, paraformaldehyde and demineralized water are added in reactor, open and stir and condensation pipe, maintaining temperature of charge is 30 ℃～40 ℃, and wherein, the consumption of paraformaldehyde is 38%～65% of phenol weight, and the consumption of demineralized water is 40%～70% of phenol weight;
(b) in above-mentioned (a), add catalyzer, be slowly warming up to 80 ℃～90 ℃, isothermal reaction 2～4h, wherein, the consumption of catalyzer is 0.5%～2% of phenol weight;
(c) after isothermal reaction 2～4h, add nertralizer, its consumption is 1～15% of phenol weight;
(d) vacuumize dehydration after having neutralized, vacuum is-0.08～-0.095MPa, in the time that system viscosity is 2000mPa ﹒ S～9000mPa ﹒ S, and cooling discharging;
Wherein, described catalyzer is one or more in NaOH, ammoniacal liquor, sodium carbonate, potash, described nertralizer is one or more in barium hydroxide, aluminium hydroxide, magnesium hydroxide, magnesia and the calcium oxide of solid granular, simultaneously, nertralizer can also absorb the moisture in resin, is conducive to the Temperature Distribution equilibrium in foam process.
In the preparation of above-mentioned foamable phenolic resins, in adding nertralizer, add formaldehyde catching agent or/and flexibilizer, the consumption of described formaldehyde catching agent is 0.5%～2% of phenol weight, the consumption of flexibilizer is 0.3%～4% of phenol weight.Wherein, described formaldehyde catching agent is one or more in urea, melamine, and described flexibilizer is one or more in ethylene glycol, Macrogol 200, polyethylene glycol 500, polyethylene glycol 800, polyethylene glycol 1500, PPG 6205, liquid nitrile rubber.
A further object of the present invention is to provide a kind of preparation method of sand clad can composite phenol formaldehyde foam heat-insulating board, and warming plate obtained by this method comprises following three layers:
Phenol formaldehyde foam layer thickness is 2～20cm,
Lining cloth layer thickness is 0.02～0.3cm,
Surface sand grains layer thickness is 0.02～0.3cm,
Wherein, lining cloth layer by pre-spraying aerodux on lining cloth through primary solidification and after form after solidifying, lining cloth layer, between phenol formaldehyde foam layer and surperficial sand grains layer, plays the effect of bonding phenol formaldehyde foam layer and surperficial sand grains layer.
A further object of the present invention is to provide a kind of two-sided sand composite phenol formaldehyde foam heat-insulating board preparation method of covering, and comprises the following steps:
(1) pre-spraying aerodux on lining cloth, then plants sand by gravitational method and forms surperficial sand grains layer, and the lining cloth that forms surperficial sand grains layer is heated and within 5～60 minutes, makes, after aerodux primary solidification, to make end liner at 90～130 ℃;
(2) end liner good primary solidification is faced down to plant sand, the non-supine mode of sand of planting is laid on mould, apply phenol formaldehyde foam feed liquid at the non-sand face of planting, then above phenol formaldehyde foam feed liquid, add the end liner that lid layer primary solidification is good, finally at 45～90 ℃, heating makes phenol formaldehyde foam feed liquid foamed solidification;
(3) form after phenol formaldehyde foam layer at phenol formaldehyde foam feed liquid foamed solidification, cooling die is to room temperature, and the then demoulding, can obtain the two-sided sand composite phenol formaldehyde foam heat-insulating board that covers.
The preparation method of a kind of sand clad can composite phenol formaldehyde foam heat-insulating board provided by the invention, realize one-step shaping legal system and made sand clad can composite phenol formaldehyde foam heat-insulating board, warming plate surface layer color can be by the color adjustment of sand grains, really integrate insulation and decorative effect, and preparation method is simple, repeating property is strong, thereby enhance productivity, in addition, due in phenol formaldehyde foam insulation feed liquid, by the use of carbon black and nertralizer, make feed liquid in foamed solidification moulding, Temperature Distribution equilibrium, can obtain the curing phenol formaldehyde foam layer of even foaming, thereby make phenol formaldehyde foam layer there is excellent heat insulating ability, mechanical strength, simultaneously under the further catalysis of curing compound, make aerodux and sand grains have stronger adhesion stress.
The specific embodiment
Below by the present invention is described in detail, the features and advantages of the invention will become more clear, clear and definite along with these explanations.
According to an aspect of the present invention, provide a kind of preparation method of sand clad can composite phenol formaldehyde foam heat-insulating board, the method comprises the following steps:
(1) pre-spraying aerodux on lining cloth, then form surperficial sand grains layer by gravitational method at the lining cloth uppper sand embedding of pre-spraying aerodux, the lining cloth that forms surperficial sand grains layer is heated and within 5～60 minutes, makes, after aerodux primary solidification, to make end liner at 90～130 ℃;
(2) end liner good primary solidification is faced down to plant sand, the non-supine mode of sand of planting is laid on mould, apply phenol formaldehyde foam feed liquid at the non-sand face of planting, then at 45～90 ℃, heating makes phenol formaldehyde foam feed liquid foamed solidification form phenol formaldehyde foam layer, and the aerodux in foamed solidification in end liner further solidifies after crosslinked carrying out;
(3) form after phenol formaldehyde foam layer at phenol formaldehyde foam feed liquid foamed solidification, cooling die is to room temperature, and the then demoulding, can obtain described sand clad can composite phenol formaldehyde foam heat-insulating board.
Wherein, described aerodux is to mix preparation by the composition that comprises following weight proportion:
100 parts, foamable phenolic resins,
2～6 parts of polyethylene glycol oxides,
Wherein, described phenol formaldehyde foam feed liquid is to mix preparation by the composition that comprises following weight proportion:
Described surfactant is to be selected from one or more in Tween-40, Tween-80, AK8812, L5440 and polyethylene glycol oxide; Described blowing agent is one or more in benzinum, pentane, pentamethylene, n-hexane and carrene; Described nertralizer is one or more in barium hydroxide, aluminium hydroxide, magnesium hydroxide, magnesia and the calcium oxide of solid granular; Described carbon black is one or more in N220, N234, N326, N330, N339, N375; Described curing compound be inorganic acid as sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, and organic acid is as one or more in formic acid, oxalic acid, p-methyl benzenesulfonic acid, xylene monosulfonic acid, pyrovinic acid and DBSA.
In above-mentioned preparation method, plant lining cloth after sand heats and within 5～60 minutes, carries out primary solidification at 90～130 ℃, for providing bonding force between lining cloth and sand grains, make that sand grains is unlikely to come off, now complete crosslinking curing of aerodux, thus keep flexible, and making to plant tamper cloth can be bending and reel, be convenient to implement the compound of follow-up and phenol formaldehyde foam, particularly in the time adopting continuous foamed technique to manufacture phenol formaldehyde foam layer, lining cloth must have the characteristic that can reel.In primary solidification process, heating-up temperature exceedes 60 minutes higher than 130 ℃ or heat time, all can cause being sprayed in advance the phenolic resins degree of cross linking on lining cloth too high, produces fragility, and what affect end liner can crimp property.
In above-mentioned preparation method, by end liner good primary solidification face down to plant sand, the non-supine mode of sand of planting is laid on mould, apply phenol formaldehyde foam feed liquid at the non-sand face of planting, then foamed solidification at 45～90 ℃, in foamed solidification, aerodux in end liner is further cross-linked and carries out rear solidifying, and form cross-linked network with phenol formaldehyde foam, for firmly adhesion stress is provided between lining cloth and phenol formaldehyde foam, the moulding of phenol formaldehyde foam feed liquid foamed solidification has been synchronizeed with rear the solidifying of aerodux.In addition, aerodux in end liner is after contacting with phenol formaldehyde foam feed liquid, at 45～90 ℃, solidify by further occurring under the catalytic action of curing compound contained in phenol formaldehyde foam feed liquid after cross-linking reaction is carried out, form integrated cross-linked network with phenol formaldehyde foam, thereby give the bonding force that sand grains is stronger simultaneously.
In the preparation of above-mentioned aerodux, use the main component of foamable phenolic resins as adhesive, make, in the time of the moulding of phenol formaldehyde foam feed liquid foamed solidification, to be better cross-linked to form Design Integrative Network Structure with phenol formaldehyde foam.In foamable phenolic resins, add polyethylene glycol oxide and can improve the pliability after aerodux primary solidification, acquisition can curling end liner.Wherein, based on the foamable phenolic resins of 100 weight portions, polyethylene glycol oxide consumption is 2～6 weight portions, if polyethylene glycol oxide consumption is lower than 2 weight portions, because polyethylene glycol oxide addition is too small, and can not play the flexible effect improving after aerodux primary solidification, thereby cause end liner fragility large, affect follow-up construction effect, otherwise, if polyethylene glycol oxide consumption is greater than 6 weight portions, can make the adhesion stress after aerodux primary solidification decline, sand grains is easily come off.
In the preparation of above-mentioned phenol formaldehyde foam feed liquid, surfactant makes foam stable homogeneous more can foam for feed liquid time, can also make the compatibility of the each component in feed liquid better simultaneously.Based on the foamable phenolic resins of 100 weight portion, dosage of surfactant is 2～6 weight portions, if dosage of surfactant is lower than 2 weight portions, can cause because consumption is too low foaming, otherwise, if dosage of surfactant, higher than 6 weight portions, can cause foaming effect bad because consumption is excessive.
In the preparation of above-mentioned phenol formaldehyde foam feed liquid, blowing agent provides the foam of good stability and cell size homogeneous while foaming for feed liquid.Based on the foamable phenolic resins of 100 weight portion, foaming agent consumption is 5～9 weight portions, if the consumption of blowing agent is lower than 5 weight portions, can cause foaming degree inadequate because foaming agent consumption is not enough, otherwise, if the consumption of blowing agent is higher than 9 weight portions, can cause because foaming dosage is excessive in gained foam abscess excessive, cause gained to cover sand foam board quality badness.
In the preparation of above-mentioned phenol formaldehyde foam feed liquid, nertralizer not only further reduces the remaining acidity of foamable phenolic resins, and can also improve the fireproof performance of phenol formaldehyde foam layer, simultaneously, can also absorb the moisture in expandable resin, thereby the Temperature Distribution while making feed liquid foamable is more even, foaming and rear curing more balanced.Based on the foamable phenolic resins of 100 weight portion, the consumption of nertralizer is 10～45 weight portions, if nertralizer consumption is lower than 10 weight portions, be difficult to and foam material liquid in remaining sour composition, the acidity of gained foam is strong, corrosivity is strong, thereby the potential safety hazard of existence, otherwise, if nertralizer consumption higher than 45 weight portions, makes the quality badness of gained sand clad can composite phenol formaldehyde foam heat-insulating board because its consumption is excessive.
In the preparation of above-mentioned phenol formaldehyde foam feed liquid, carbon black is Powdered, particle is thin, specific area is large, and the thermal conductive network forming in feed liquid contributes to feed liquid in the time that foamable solidifies, and heat conduction is carried out in feed liquid inside, dwindle the temperature difference, while avoiding foaming, cause abscess to break and coalescence because local temperature is too high, produce large abscess, thereby affect heat insulating ability and the mechanical strength of phenol formaldehyde foam layer.Based on the foamable phenolic resins of 100 weight portion, the consumption of carbon black is 0.2～3 part, and in this weight portion, carbon black can form a thermal conductive network, and good heat conduction effect makes after feed liquid heating, Temperature Distribution equilibrium, thus make foam stable homogeneous, do not break.If parts by weight are lower than 0.2 part, due to consumption very little, heat-conducting effect is bad, if umber is greater than 3 parts, again can be too much because of consumption, affect the combination property of phenol formaldehyde foam layer, as heat insulating ability, mechanical strength.
In the preparation of above-mentioned phenol formaldehyde foam feed liquid, based on the foamable phenolic resins of 100 weight portion, hardener dose is 10～25 weight portions.If hardener dose is lower than 10 weight portions, because the too low meeting of hardener dose causes foam curing degree inadequate, otherwise, if hardener dose is higher than 25 weight portions, cause curing rate too fast because hardener dose is too high, gained covers the quality badness of sand foam board.In addition, curing compound also plays the rear curing effect at 45～90 ℃ of catalysed phenolic resin adhesive, makes to form integrated cross-linked network with phenol formaldehyde foam layer, thereby gives the adhesion stress that sand grains is larger.
In a preferred embodiment, curing compound is the mixture of p-methyl benzenesulfonic acid or p-methyl benzenesulfonic acid and sulfuric acid, and effect curing after the solidification effect of the mixture of p-methyl benzenesulfonic acid or p-methyl benzenesulfonic acid and sulfuric acid and catalysis is better.
In a preferred embodiment, surfactant in phenol formaldehyde foam feed liquid is 3～4 weight portions preferably, in this weight portion, play best stable foam and the effect that makes cell size homogeneous, blowing agent is 5～8 weight portions preferably, in this weight portion, can obtain the foam of optimal stability, nertralizer is 10～20 weight portions preferably, in this weight portion, can obtain acid low phenol formaldehyde foam, reduce body of wall and the corrosion of metallic steel shelf structure around, thus the potential safety hazard of avoiding.
In a preferred embodiment, after end liner is laid on mould, be preheated to after 30～40 ℃, apply fast phenol formaldehyde foam feed liquid at the non-sand face of planting of end liner, then put into the baking oven foamed solidification of 60～80 ℃.Mould and end liner are preheated to 30～40 ℃ in advance, and the temperature difference can reduce with the moulding of phenol formaldehyde foam feed liquid foamed solidification time, is conducive to heat insulating ability, the mechanical property of phenol formaldehyde foam layer.
In a preferred embodiment, lining cloth is one or more in nonwoven, glass fabric, textile sheet, lining cloth is as matrix, and its water resistance, abrasion resistance and pliability are all better than using paper as matrix, and sand grains is one or more in river sand, extra large sand, ore in sand form, artificially colored color sand.
According to a further aspect in the invention, foamable phenolic resins is by comprising the following steps preparation:
(a) phenol, paraformaldehyde and demineralized water are added in reactor, open and stir and condensation pipe, maintaining temperature of charge is 30 ℃～40 ℃, and wherein, the consumption of paraformaldehyde is 38%～65% of phenol weight, and the consumption of demineralized water is 40%～70% of phenol weight;
(b) in above-mentioned (a), add catalyzer, be slowly warming up to 80 ℃～90 ℃, isothermal reaction 2～4h, wherein, the consumption of catalyzer is 0.5%～2% of phenol weight;
(c) after isothermal reaction 2～4h, add nertralizer, its consumption is 1～15% of phenol weight;
(d) vacuumize dehydration after having neutralized, vacuum is-0.08～-0.095MPa, in the time that system viscosity is 2000mPa ﹒ S～9000mPa ﹒ S, and cooling discharging; Wherein,
Described catalyzer is one or more in NaOH, ammoniacal liquor, sodium carbonate, potash, one or more in barium hydroxide, aluminium hydroxide, magnesium hydroxide, magnesia and calcium oxide that described nertralizer is solid granular.
In the preparation of above-mentioned foamable phenolic resins, phenolic resins is to carry out condensation polymerization by phenol and paraformaldehyde to prepare.Wherein, paraformaldehyde replaces general industry formalin to carry out condensation polymerization reaction, both can reduce the energy consumption of dewatering in reaction, can greatly reduce again wastewater treatment capacity, thereby reach the effect of environmental protection.
In the preparation of above-mentioned foamable phenolic resins, nertralizer particle is coated by the phenolic resins that is generated in phenol formaldehyde condensation polymerization process, after phenol formaldehyde foam feed liquid is during through foamed solidification moulding, can there is neutralization reaction fast with the acid of retaining after the moulding of phenol formaldehyde foam feed liquid foamed solidification in the nertralizer particle that these are wrapped by, thereby consume the acid of retaining in phenol formaldehyde foam feed liquid, therefore above-mentioned foamable phenolic resins is suitable for preparing low acid phenol formaldehyde foam, reduced to metope and and the corrosivity of corollary equipment, thereby reduce potential safety hazard.
In the preparation of above-mentioned foamable phenolic resins, in adding nertralizer, add formaldehyde catching agent or/and flexibilizer, the consumption of described formaldehyde catching agent is 0.5%～2% of phenol weight, the consumption of flexibilizer is 0.3%～4% of phenol weight.Wherein, described formaldehyde catching agent is one or more in urea, melamine, can remove free formaldehyde, reach environmental protection and do not affect the insulation of phenol formaldehyde foam layer and the effect of abrasion resistance, described flexibilizer is one or more in ethylene glycol, Macrogol 200, polyethylene glycol 500, polyethylene glycol 800, polyethylene glycol 1500, PPG 6205, liquid nitrile rubber, makes phenol formaldehyde foam layer pliability good.
In accordance with a further aspect of the present invention, a kind of sand clad can composite phenol formaldehyde foam heat-insulating board obtaining by preparation method provided by the invention, comprises following three layers:
Phenol formaldehyde foam layer thickness is 2～20cm,
Lining cloth layer thickness is 0.02～0.3cm,
Surface sand grains layer thickness is 0.02～0.3cm,
Wherein, lining cloth layer by pre-spraying aerodux on lining cloth through primary solidification and after form after solidifying, lining cloth layer, between phenol formaldehyde foam layer and surperficial sand grains layer, plays the effect of bonding phenol formaldehyde foam layer and surperficial sand grains layer.
In above-mentioned a kind of sand clad can composite phenol formaldehyde foam heat-insulating board, for thermal and insulating performance is provided, phenol formaldehyde foam layer thickness should not be lower than 2cm, and concrete thickness can regulate by the amount of application of phenol formaldehyde foam feed liquid in the distance between mould bottom surface and the end face of foaming use and unit area.In addition, when the spraying of aerodux in lining cloth layer, to guarantee that adhesive uniform fold lives lining cloth, but be difficult for blocked uply, otherwise can affect adhesion stress.
In accordance with a further aspect of the present invention, provide a kind of two-sided sand composite phenol formaldehyde foam heat-insulating board preparation method of covering, comprise the following steps:
(1) pre-spraying aerodux on lining cloth, then plants sand by gravitational method and forms surperficial sand grains layer, and the lining cloth that forms surperficial sand grains layer is heated and within 5～60 minutes, makes, after aerodux primary solidification, to make end liner at 90～130 ℃;
(2) end liner good primary solidification is faced down to plant sand, the non-supine mode of sand of planting is laid on mould, apply phenol formaldehyde foam feed liquid at the non-sand face of planting, then above phenol formaldehyde foam feed liquid, add the end liner that lid layer primary solidification is good, finally at 45～90 ℃, heating makes phenol formaldehyde foam feed liquid foamed solidification;
(3) form after phenol formaldehyde foam layer at phenol formaldehyde foam feed liquid foamed solidification, cooling die is to room temperature, and the then demoulding, can obtain the two-sided sand composite phenol formaldehyde foam heat-insulating board that covers.
Described two-sided covering in sand composite phenol formaldehyde foam heat-insulating board, the two-sided sand that covers of warming plate is in order to provide thermal and insulating performance, phenol formaldehyde foam layer thickness should not be lower than 2cm, and in distance when concrete thickness can be by foaming between mould bottom surface and end face and unit area, the amount of application of foamable phenolic resins regulates.
Embodiment
Further describe the present invention by instantiation below.But these examples are only exemplary, protection scope of the present invention are not formed to any restriction.
In following embodiment and comparative example:
Paraformaldehyde (Paraformaldehyde): CAS NO.:30525-89-4, Jinan century sensible Chemical Co., Ltd..
Embodiment 1
(1) get 0.5 square metre of the nonwoven that every square metre of quality is 60g, on got nonwoven, evenly spray urea formaldehyde adhesive, then on the lining cloth of spraying aerodux, cover that to spread average diameter be the river sand 400g of 0.5 millimeter, make river sand uniform fold adhesive form surperficial sand grains layer, then be placed in 110 ℃ of baking ovens and heat 20 minutes, obtain end liner;
(2) above-mentioned end liner is faced down to plant sand, the non-supine mode of sand of planting is laid in and is laid in inner chamber thickness as the mold bottom of 5 centimetres, by mould and die preheating to 40 ℃, apply fast phenol formaldehyde foam feed liquid at the non-sand face of planting, then at 80 ℃, heating makes phenol formaldehyde foam feed liquid foamed solidification form phenol formaldehyde foam layer;
(3) form after phenol formaldehyde foam layer at phenol formaldehyde foam feed liquid foamed solidification, take out mold cools down to room temperature, the then demoulding, obtains sand clad can composite phenol formaldehyde foam heat-insulating board;
Wherein, aerodux is evenly mixed and makes by the foamable phenolic resins of 65g and 1.5g polyethylene glycol oxide,
Wherein, phenol formaldehyde foam feed liquid is by the foamable phenolic resins of 200g, 6g Tween-80, and 20g aluminum hydroxide particles, 1g carbon black N339 joins and in reactor, stirs 5min together with 10g pentane, then adds 22g p-methyl benzenesulfonic acid rapid stirring together, and mix and make,
Wherein, foamable phenolic resins is added in 5L four-hole boiling flask by 1200g phenol, 450g paraformaldehyde and 500g demineralized water, opens and stirs and condensation pipe, and holding temperature is at 30 ℃～40 ℃, then add 6g NaOH, slowly be warming up to 80 ℃～90 ℃, isothermal reaction 4h, adds 12g melamine and 60g aluminium hydroxide, vacuumize dehydration, vacuum is at-0.08～-0.095MPa, and when system viscosity reaches 2000mPa ﹒ S, cooling discharging makes.
Embodiment 2
(1) get 0.5 square metre of the glass-fiber-fabric that every square metre of quality is 120g, on got nonwoven, evenly spray urea formaldehyde adhesive, then on the lining cloth of spraying aerodux, cover that to spread average diameter be the extra large sand 500g of 0.5 millimeter, make extra large sand uniform fold adhesive form surperficial sand grains layer, then be placed in 120 ℃ of baking ovens and heat 15 minutes, obtain end liner;
(2) above-mentioned end liner is faced down to plant sand, the non-supine mode of sand of planting is laid in and is laid in inner chamber thickness as the mold bottom of 10 centimetres, by mould and die preheating to 45 ℃, apply fast phenol formaldehyde foam feed liquid at the non-sand face of planting, then at 70 ℃, heating makes phenol formaldehyde foam feed liquid foamed solidification form phenol formaldehyde foam layer;
(3) form after phenol formaldehyde foam layer at phenol formaldehyde foam feed liquid foamed solidification, take out mold cools down to room temperature, the then demoulding, obtains sand clad can composite phenol formaldehyde foam heat-insulating board; Wherein, described aerodux is evenly mixed to get by the foamable phenolic resins of 70g and 2g polyethylene glycol oxide;
Wherein, described phenol formaldehyde foam feed liquid is by the foamable phenolic resins of 400g gained, 12g Tween-40,80g aluminum hydroxide particles, 4g carbon black N220 joins and in reactor, stirs 5min together with 28g pentane, then adds 28g sulfuric acid rapid stirring together with 12g p-methyl benzenesulfonic acid, mix and make
Wherein, foamable phenolic resins is added in 5L four-hole boiling flask by 1200g phenol, 690g paraformaldehyde and 750g demineralized water, opens and stirs and condensation pipe, and holding temperature is at 30 ℃～40 ℃, add 8.5g magnesia, slowly be warming up to 80 ℃～90 ℃, isothermal reaction 3h, adds 24gPEG-1500 and 150g aluminium hydroxide, vacuumize dehydration, vacuum is at-0.08～-0.095MPa, and when system viscosity reaches 4000mPa ﹒ S, cooling discharging makes.
Comparative example
Comparative example 1
Repeat embodiment 1, wherein, aerodux is the foamable phenolic resins of 65g.
Comparative example 2
Repeat embodiment 2, wherein, the lining cloth that has surperficial sand grains layer to form is placed in to 140 ℃ of baking ovens and heats 15 minutes.
Comparative example 3
Repeat embodiment 2, wherein, in described phenol formaldehyde foam feed liquid, do not add carbon black N220.
Comparative example 4
Repeat embodiment 2, wherein, in described phenol formaldehyde foam, the addition of carbon black N220 is 13g.
Test example
end liner bending property is measured
Gained end liner is reeled 2 layers at diameter to plant the outside mode of layer of sand on the cylinder of 10cm, then take off in the non-outside mode of layer of sand of planting and again on same cylinder, reel 2 layers, complete the circulation of a positive and negative coiling, observation lining cloth configuration of surface after the circulation of carrying out reeling for 5 times.
By embodiment 1, embodiment 2, in comparative example 1 and comparative example 2, the end liner of gained does respectively bending property mensuration, and result is as shown in table 1:
Table 1
the performance test of phenolic foam heat insulation plate
According to warming plate density, compressive strength, bend fracture power and water absorption rate in the each embodiment of GB/T20974-2007 standard test and comparative example, result is as shown in table 2:
Table 2
In conjunction with the specific embodiment and exemplary example, the present invention is had been described in detail above, but these explanations can not be interpreted as limitation of the present invention.It will be appreciated by those skilled in the art that in the situation that not departing from spirit and scope of the invention, can carry out multiple replacement of equal value, modify or improve technical solution of the present invention and embodiment thereof, these all fall within the scope of the present invention.Protection scope of the present invention is as the criterion with claims.
Claims (10)
1. a preparation method for sand clad can composite phenol formaldehyde foam heat-insulating board, the method comprises the following steps:
(1) pre-spraying aerodux on lining cloth, then form surperficial sand grains layer by gravitational method at the lining cloth uppper sand embedding of pre-spraying aerodux, the lining cloth that forms surperficial sand grains layer is heated and within 5～60 minutes, makes, after aerodux primary solidification, to make end liner at 90～130 ℃;
(2) end liner good primary solidification is faced down to plant sand, the non-supine mode of sand of planting is laid on mould, apply phenol formaldehyde foam feed liquid at the non-sand face of planting, then at 45～90 ℃, heating makes phenol formaldehyde foam feed liquid foamed solidification form phenol formaldehyde foam layer, in foamed solidification, the aerodux in end liner is further cross-linked and carries out rear solidifying;
(3) form after phenol formaldehyde foam layer at phenol formaldehyde foam feed liquid foamed solidification, cooling die is to room temperature, and the then demoulding, can obtain described sand clad can composite phenol formaldehyde foam heat-insulating board;
Wherein, described aerodux is to mix preparation by the composition that comprises following weight proportion:
100 parts, foamable phenolic resins,
2～6 parts of polyethylene glycol oxides,
Wherein, described phenol formaldehyde foam feed liquid is to mix preparation by the composition that comprises following weight proportion:
Wherein, described surfactant is to be selected from one or more in Tween-40, Tween-80, AK8812, L5440 and polyethylene glycol oxide; Described blowing agent is one or more in benzinum, pentane, pentamethylene, n-hexane and carrene; Described nertralizer is one or more in barium hydroxide, aluminium hydroxide, magnesium hydroxide, magnesia and the calcium oxide of solid granular; Described carbon black is one or more in N220, N234, N326, N330, N339, N375; Described curing compound be inorganic acid as sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, and organic acid is as one or more in formic acid, oxalic acid, p-methyl benzenesulfonic acid, xylene monosulfonic acid, pyrovinic acid and DBSA.
2. the preparation method of a kind of sand clad can composite phenol formaldehyde foam heat-insulating board according to claim 1, is characterized in that, the mixture of the preferred p-methyl benzenesulfonic acid of described curing compound or p-methyl benzenesulfonic acid and sulfuric acid.
3. the preparation method of a kind of sand clad can composite phenol formaldehyde foam heat-insulating board according to claim 1, is characterized in that, described surfactant is 3～4 weight portions preferably, and blowing agent is 5～8 weight portions preferably, and nertralizer is 10～20 weight portions preferably.
4. the preparation method of a kind of sand clad can composite phenol formaldehyde foam heat-insulating board according to claim 1, it is characterized in that, in step (2), after end liner is laid on mould, be preheated to after 30～40 ℃, the non-sand face of planting at end liner applies phenol formaldehyde foam feed liquid fast, then puts into the baking oven foamed solidification of 60～80 ℃.
5. the preparation method of a kind of sand clad can composite phenol formaldehyde foam heat-insulating board according to claim 1, it is characterized in that, described lining cloth is one or more in nonwoven, glass fabric, textile sheet, and the sand grains in described surperficial sand grains layer is one or more in river sand, extra large sand, ore in sand form, artificially colored color sand.
6. the preparation method of a kind of sand clad can composite phenol formaldehyde foam heat-insulating board according to claim 1, is characterized in that, foamable phenolic resins is by comprising the following steps preparation:
(a) phenol, paraformaldehyde and demineralized water are added in reactor, open and stir and condensation pipe, maintaining temperature of charge is 30 ℃～40 ℃, and wherein, the consumption of paraformaldehyde is 38%～65% of phenol weight, and the consumption of demineralized water is 40%～70% of phenol weight;
(b) in above-mentioned (a), add catalyzer, be slowly warming up to 80 ℃～90 ℃, isothermal reaction 2～4h, wherein, the consumption of catalyzer is 0.5%～2% of phenol weight;
(c) after isothermal reaction 2～4h, add nertralizer, its consumption is 1～15% of phenol weight;
(d) vacuumize dehydration after having neutralized, vacuum is-0.08～-0.095MPa, in the time that system viscosity is 2000mPa ﹒ S～9000mPa ﹒ S, and cooling discharging;
Wherein, described catalyzer is one or more in NaOH, ammoniacal liquor, sodium carbonate, potash, one or more in barium hydroxide, aluminium hydroxide, magnesium hydroxide, magnesia and calcium oxide that described nertralizer is solid granular.
7. the preparation method of a kind of sand clad can composite phenol formaldehyde foam heat-insulating board according to claim 6, it is characterized in that, in the preparation of foamable phenolic resins, in adding nertralizer, add formaldehyde catching agent or/and flexibilizer, wherein, the consumption of described formaldehyde catching agent is 0.5%～2% of phenol weight, and the consumption of flexibilizer is 0.3%～4% of phenol weight.
8. the preparation method of a kind of sand clad can composite phenol formaldehyde foam heat-insulating board according to claim 7, it is characterized in that, described formaldehyde catching agent is one or more in urea, melamine, and described flexibilizer is one or more in ethylene glycol, Macrogol 200, polyethylene glycol 500, polyethylene glycol 800, polyethylene glycol 1500, PPG 6205, liquid nitrile rubber.
9. the preparation method of a kind of sand clad can composite phenol formaldehyde foam heat-insulating board according to claim 1, is characterized in that, described warming plate comprises following three layers:
Phenol formaldehyde foam layer thickness is 2～20cm,
Lining cloth layer thickness is 0.02～0.3cm,
Surface sand grains layer thickness is 0.02～0.3cm,
Wherein, lining cloth layer by pre-spraying aerodux on lining cloth through primary solidification and after form after solidifying, lining cloth layer, between phenol formaldehyde foam layer and surperficial sand grains layer, plays the effect of bonding phenol formaldehyde foam layer and surperficial sand grains layer.
10. the two-sided sand composite phenol formaldehyde foam heat-insulating board preparation method of covering, comprises the following steps:
(1) pre-spraying aerodux on lining cloth, then plants sand by gravitational method and forms surperficial sand grains layer, and the lining cloth that forms surperficial sand grains layer is heated and within 5～60 minutes, makes, after aerodux primary solidification, to make end liner at 90～130 ℃;
(2) end liner good primary solidification is faced down to plant sand, the non-supine mode of sand of planting is laid on mould, apply phenol formaldehyde foam feed liquid at the non-sand face of planting, then above phenol formaldehyde foam feed liquid, add the end liner that lid layer primary solidification is good, finally at 45～90 ℃, heating makes phenol formaldehyde foam feed liquid foamed solidification;
(3) form after phenol formaldehyde foam layer at phenol formaldehyde foam feed liquid foamed solidification, cooling die is to room temperature, and the then demoulding, can obtain the two-sided sand composite phenol formaldehyde foam heat-insulating board that covers.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105295776A (en) * | 2015-10-09 | 2016-02-03 | 太仓市世佳实业有限公司 | Bonding foaming adhesive and application thereof in insulation board system |
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