CN103866871B - A kind of preparation method of sand clad can composite phenol formaldehyde foam heat-insulating board - Google Patents
A kind of preparation method of sand clad can composite phenol formaldehyde foam heat-insulating board Download PDFInfo
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- CN103866871B CN103866871B CN201410119544.XA CN201410119544A CN103866871B CN 103866871 B CN103866871 B CN 103866871B CN 201410119544 A CN201410119544 A CN 201410119544A CN 103866871 B CN103866871 B CN 103866871B
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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 present invention relates to a kind of preparation method of sand clad can composite phenol formaldehyde foam heat-insulating board, the method comprises: pre-spraying after aerodux on lining cloth, plant sand by gravitational method, 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, rear the solidifying and end liner and froth bed integrated bonding of simultaneously realizing phenol aldehyde adhesive, the cooling rear demoulding. In addition, also can make the two-sided sand composite phenol formaldehyde foam heat-insulating board that covers. Method provided by the present invention completes wall decoration in realizing heat preservation construction.
Description
Technical field
The present invention relates to building thermal insulation material, be specifically related to one and there is sand clad can againClose the preparation method of phenolic foam composite insulation board.
Background technology
Traditional phenolic foam heat insulation plate used for building exterior wall is being installed after wall, need to beThe outer surface of warming plate applies cement mortar and carries out incrustation. This construction methodComplex process, site operation workload is large, long in time limit, efficiency is low, and construction matterAmount is subject to job site condition and workmen's artificial factors, and wall insulation system is executedWorking medium amount easily fluctuates. In recent years, there is surperficial coating cement mortar or other are inorganicThe composite phenol formaldehyde foam heat-insulating board of coating, has simplified wall thermal insulating work progress.
WO2002038879A1 (2002) and CN1586849A(2005) discloseApply the composite insulation boards of cement mortar on phenolic foam board surface.DE202011001989 (2011) discloses at warming plate surface bonding glass fiber thenApply the method for cement mortar. CN202577625U (2012) utility model discloses onePlant the composite insulation boards of inorganic material coating organic material, by perfusion or bonding modeBy compound to inorganic material heat-insulation layer and organic material central layer. CN102515641A (2012)Disclose fire-retardant cement-based interface mat for a kind of exterior-wall heat insulation, its preparation technology is:Silica flour, solid flame retardant, cement mixing is even, make inorganic powder; By heightMolecularly Imprinted Polymer emulsion, deionized water, defoamer, bactericide mix, and makePolymer agent material; Inorganic powder and polymer agent material are uniformly mixed, make resistanceCombustion cement-based interface slurry, is then applied to glass fibre belt table by cement-based interface slurryFace, dries and makes fire-retardant cement-based interface mat for exterior-wall heat insulation, hard for being compounded inThe organic insulation material surfaces such as bubble polyurethane, phenolic aldehyde, XPS, improve warming plate surfaceAnti-flammability. CN203022145U(2012) utility model provides a kind of compoundThe phenolic foam heat insulation plate of fire proofing, this warming plate is outside phenolic foam heat insulation plateAfter applying one deck interfacial agents on surface, apply again one deck fire proofing, strengthened plate bodySurface strength, has improved the fire retardant performance of plate body. CN102704586A(2012)Disclose a kind of modified phenolic composite insulation boards, comprised modified phenolic warming plate, interfaceAgent layer and quartz sand layer, the upper and lower faces of modified phenolic warming plate is respectively equipped with interfaceAgent layer, interfacial agents layer is provided with quartz sand layer; Smear modified phenolic warming plate is two-sidedInterfacial agents, then two-sided compound quartz sand, finally dries solidChange. CN203347037U (2013) utility model discloses a kind of exterior wall for building and has protectedTemperature plate, this warming plate comprises phenol formaldehyde foam core layer and is positioned at phenol formaldehyde foam core layer oneThe cement-based coiled material layer of side or both sides, cement-based coiled material layer and phenol formaldehyde foam core layer are solidFixed connection. The composite phenol formaldehyde foam heat-insulating board of these patent reports, has simplified phenolic aldehyde bubbleThe work progress of foam exterior wall heat-preserving system, and finish coat can carry out batch production designCustomization, the construction quality of effective guarantee wall insulation system. But, according to existingComposite phenol formaldehyde foam thermal insulation board fabrication method, screed and architectural surface are all to obtainAfter phenol formaldehyde foam sheet material finished product, carry out follow-up Compound Machining, first obtain phenolic foam boardMaterial, then applies mortar or decorative layer is adhered to sheet material with adhesive at plate surfaceSurface. This division system making method complex process, occupation of land is many, and production efficiency is low, workPeople'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 that a kind of cost is low, production efficiency is high badlyMaterial manufacture method, the method should be able to obtain by easy technique the sand of excellent performanceThe pnenolic aldehyde foam heat-insulating board of clad can.
Summary of the invention
In order to solve problems of the prior art, the inventor has carried out grinding with keen determinationStudy carefully, found that: on lining cloth, after pre-spraying aerodux, pass through gravityMethod, at the lining cloth uppper sand embedding of pre-spraying aerodux, then heats primary solidificationAfter make end liner, plant sand face end liner non-and apply phenol formaldehyde foam feed liquid, then heatingCarry out foamed solidification and form phenol formaldehyde foam layer, realize the rear of phenol aldehyde adhesive simultaneously and solidifyAnd end liner and froth bed is integrated bonding, the cooling rear demoulding, can obtain sand and coverFace composite phenol formaldehyde foam heat-insulating board, thus the present invention completed.
The object of the present invention is to provide a kind of sand clad can composite phenol formaldehyde foam heat-insulating boardPreparation method, the method comprises the following steps:
(1) pre-spraying aerodux on lining cloth, then exists by gravitational methodThe lining cloth uppper sand embedding of pre-spraying aerodux forms surperficial sand grains layer, will formThe lining cloth of surface sand grains layer heats at 90～130 DEG C makes phenolic resins sticky for 5～60 minutesAfter mixture primary solidification, make end liner;
(2) end liner good primary solidification is faced down to plant sand, the non-sand of planting is supineMode is laid on mould, applies phenol formaldehyde foam feed liquid at the non-sand face of planting, and then existsAt 45～90 DEG C, heating makes phenol formaldehyde foam feed liquid foamed solidification form phenol formaldehyde foam layer,Aerodux when foamed solidification in end liner further crosslinked carry out rear solidChange;
(3) form after phenol formaldehyde foam layer cooling frame at phenol formaldehyde foam feed liquid foamed solidificationTool is to room temperature, and the then demoulding, can obtain described sand clad can composite phenol formaldehyde foam and protectTemperature plate;
Wherein, described aerodux is by the composition that comprises following weight proportionMix preparation:
100 parts, foamable phenolic resins,
2～6 parts of polyethylene glycol oxides,
Wherein, described phenol formaldehyde foam feed liquid is mixed by the composition that comprises following weight proportionClose even preparation:
Wherein, described surfactant for be selected from Tween-40, Tween-80, AK8812,One or more in L5440 and polyethylene glycol oxide; Described blowing agent be benzinum,One or more in pentane, pentamethylene, n-hexane and carrene; Described neutralizationAgent be solid granular barium hydroxide, aluminium hydroxide, magnesium hydroxide, magnesia andOne or more in calcium oxide; Described carbon black be N220, N234, N326, N330,One or more in N339, N375; Described curing agent is that inorganic acid is as sulfuric acid, saltAcid, phosphoric acid, nitric acid, and organic acid is as formic acid, oxalic acid, p-methyl benzenesulfonic acid, diformazanOne or more in benzene sulfonic acid, pyrovinic acid and DBSA.
In the preparation of phenol formaldehyde foam feed liquid, the preferred p-methyl benzenesulfonic acid of described curing agent orThe mixture of person's p-methyl benzenesulfonic acid and sulfuric acid.
In the preparation of phenol formaldehyde foam feed liquid, described surfactant is 3～4 weight preferablyPart, 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, the end of byAfter lining is laid on mould, be preheated to after 30～40 DEG C, fast at the non-sand face of planting of end linerSpeed applies phenol formaldehyde foam feed liquid, then puts into the baking oven foamed solidification of 60～80 DEG C.
In the present invention, described lining cloth is nonwoven, glass fabric, braided fiberOne or more in cloth, sand grains is river sand, extra large sand, ore in sand form, artificially colored color sandIn a kind of 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 stirringAnd condenser pipe, maintaining temperature of charge is 30 DEG C～40 DEG C, wherein, and the use of paraformaldehydeAmount for phenol weight 38%～65%, the consumption of demineralized water be 40% of phenol weight～70%；
(b) in above-mentioned (a), add catalyst, be slowly warming up to 80 DEG C～90 DEG C,Isothermal reaction 2～4h, wherein, the consumption of catalyst is 0.5%～2% of phenol weight;
(c) after isothermal reaction 2～4h, add nertralizer, its consumption is phenol weight1～15%;
(d) vacuumize dehydration after having neutralized, vacuum is-0.08～-0.095MPa,In the time that system viscosity is 2000mPa ﹒ S～9000mPa ﹒ S, cooling discharging;
Wherein, described catalyst is in NaOH, ammoniacal liquor, sodium carbonate, potashOne or more, barium hydroxide, hydroxide that described nertralizer is solid granularOne or more in aluminium, magnesium hydroxide, magnesia and calcium oxide, meanwhile, neutralizationAgent can also absorb the moisture in resin, is conducive to Temperature Distribution in foam process equalWeighing apparatus.
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 phenol weight0.5%～2% of amount, the consumption of flexibilizer is 0.3%～4% of phenol weight. Wherein,Described formaldehyde catching agent is one or more in urea, melamine, described toughness reinforcingAgent is ethylene glycol, Macrogol 200, polyethylene glycol 500, polyethylene glycol 800, poly-secondOne or more in glycol 1500, PPG 6205, liquid nitrile rubber.
A further object of the present invention is to provide a kind of sand clad can composite phenol formaldehyde foam to protectThe preparation method of temperature plate, 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 the beginning of spraying in advance aerodux process on lining clothStep is solidified and rear curing rear formation, and lining cloth layer is positioned at phenol formaldehyde foam layer and surperficial sand grains layerBetween, play 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 that covers to protectTemperature plate preparation method, comprises the following steps:
(1) pre-spraying aerodux on lining cloth, then plants by gravitational methodSand forms surperficial sand grains layer, and the lining cloth that forms surperficial sand grains layer is added at 90～130 DEG CHeat makes, after aerodux primary solidification, to make end liner for 5～60 minutes;
(2) end liner good primary solidification is faced down to plant sand, the non-sand of planting is supineMode is laid on mould, applies phenol formaldehyde foam feed liquid, then at phenol at the non-sand face of plantingAldehyde foam material liquid top adds the end liner that lid layer primary solidification is good, finally at 45～90 DEG CLower heating makes phenol formaldehyde foam feed liquid foamed solidification;
(3) form after phenol formaldehyde foam layer cooling frame at phenol formaldehyde foam feed liquid foamed solidificationTool 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 side of a kind of sand clad can composite phenol formaldehyde foam heat-insulating board provided by the inventionMethod, has realized one-step shaping legal system and has made sand clad can composite phenol formaldehyde foam heat-insulating board, protectsTemperature plate surface layer color can be by the color adjustment of sand grains, real collection insulation and decorative effectIn one, and preparation method is simple, and repeating property is strong, produces thereby improveEfficiency, in addition, due in phenol formaldehyde foam insulation feed liquid, by carbon black and nertralizerUse, make feed liquid in foamed solidification moulding, Temperature Distribution equilibrium, can obtainThe phenol formaldehyde foam layer that even foaming is curing, thus it is excellent that phenol formaldehyde foam layer is hadHeat insulating ability, mechanical strength under the further catalysis of curing agent, makes phenolic aldehyde simultaneouslyResin binder and sand grains have stronger cohesive force.
Detailed description of the invention
Below by the present invention is described in detail, the features and advantages of the invention willBecome more clear, clear and definite along with these explanations.
According to an aspect of the present invention, provide a kind of sand clad can composite phenol formaldehyde foam to protectThe preparation method of temperature plate, the method comprises the following steps:
(1) pre-spraying aerodux on lining cloth, then exists by gravitational methodThe lining cloth uppper sand embedding of pre-spraying aerodux forms surperficial sand grains layer, will formThe lining cloth of surface sand grains layer heats at 90～130 DEG C makes phenolic resins sticky for 5～60 minutesAfter mixture primary solidification, make end liner;
(2) end liner good primary solidification is faced down to plant sand, the non-sand of planting is supineMode is laid on mould, applies phenol formaldehyde foam feed liquid at the non-sand face of planting, and then existsAt 45～90 DEG C, heating makes phenol formaldehyde foam feed liquid foamed solidification form phenol formaldehyde foam layer,Aerodux when foamed solidification in end liner further crosslinked carry out rear solidChange;
(3) form after phenol formaldehyde foam layer cooling frame at phenol formaldehyde foam feed liquid foamed solidificationTool is to room temperature, and the then demoulding, can obtain described sand clad can composite phenol formaldehyde foam and protectTemperature plate.
Wherein, described aerodux is by the composition that comprises following weight proportionMix preparation:
100 parts, foamable phenolic resins,
2～6 parts of polyethylene glycol oxides,
Wherein, described phenol formaldehyde foam feed liquid is mixed by the composition that comprises following weight proportionClose even preparation:
Described surfactant is for being selected from Tween-40, Tween-80, AK8812, L5440With one or more in polyethylene glycol oxide; Described blowing agent be benzinum, pentane,One or more in pentamethylene, n-hexane and carrene; Described nertralizer is for solidThe granular barium hydroxide of body, aluminium hydroxide, magnesium hydroxide, magnesia and calcium oxideIn one or more; Described carbon black be N220, N234, N326, N330, N339,One or more in N375; Described curing agent is that inorganic acid is as sulfuric acid, hydrochloric acid, phosphorusAcid, nitric acid, and organic acid as formic acid, oxalic acid, p-methyl benzenesulfonic acid, xylene monosulfonic acid,One or more in pyrovinic acid and DBSA.
In above-mentioned preparation method, plant lining cloth after sand at 90～130 DEG C, heat 5～Within 60 minutes, carry out primary solidification, for providing bonding force between lining cloth and sand grains, make sand grainsUnlikely coming off, the now incomplete crosslinking curing of aerodux, thus keepFlexibility, making to plant tamper cloth can be bending and reel, and is convenient to implement follow-up and phenol formaldehyde foamCompound, particularly in the time adopting continuous foamed technique to manufacture phenol formaldehyde foam layer, lining cloth mustMust there is the characteristic that can reel. In primary solidification process, heating-up temperature is higher than 130 DEG COr the heat time exceed 60 minutes, all can cause being sprayed in advance the phenolic resins on lining clothThe degree of cross linking is 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, applies phenol formaldehyde foam at the non-sand face of plantingFeed liquid, then foamed solidification at 45～90 DEG C, in foamed solidification, end linerIn aerodux further crosslinkedly carry out rear solidifying, and with phenol formaldehyde foam shapeBecome cross-linked network, for firmly cohesive force, phenolic aldehyde are provided between lining cloth and phenol formaldehyde foamThe moulding of foam material liquid foamed solidification has been synchronizeed with rear the solidifying of aerodux.In addition, the aerodux in end liner after contacting with phenol formaldehyde foam feed liquid,At 45～90 DEG C, by the catalytic action of curing agent contained in phenol formaldehyde foam feed liquidThe lower cross-linking reaction that further occurs is carried out rear solidifying, and forms one with phenol formaldehyde foam simultaneouslyThe cross-linked network of changing, thus give the bonding force that sand grains is stronger.
In the preparation of above-mentioned aerodux, use foamable phenolic aldehyde treeFat, as the main component of adhesive, makes in the moulding of phenol formaldehyde foam feed liquid foamed solidificationTime, be better cross-linked to form Design Integrative Network Structure with phenol formaldehyde foam. FoamableIn phenolic resins, add polyethylene glycol oxide and can improve aerodux primary solidificationAfter pliability, acquisition can curling end liner. Wherein, foaming based on 100 weight portionsPhenolic resins, polyethylene glycol oxide consumption is 2～6 weight portions, if polyethylene glycol oxideConsumption, lower than 2 weight portions, because polyethylene glycol oxide addition is too small, changes and can not playFlexible effect after kind aerodux primary solidification, thus end liner causedFragility is large, affects follow-up construction effect, otherwise, if polyethylene glycol oxide consumption is greater than 6Weight portion, can make the cohesive force after aerodux primary solidification decline,Sand grains is easily come off.
In the preparation of above-mentioned phenol formaldehyde foam feed liquid, surfactant can be sent out for feed liquidWhen bubble, make foam stable homogeneous more, can also make the each component in feed liquid simultaneouslyCompatibility better. Based on the foamable phenolic resins of 100 weight portion, surfactantConsumption is 2～6 weight portions, if dosage of surfactant lower than 2 weight portions, can be byCannot foam in too low causing of consumption, otherwise, if dosage of surfactant is higher than 6Weight portion, can cause foaming effect bad because consumption is excessive.
In the preparation of above-mentioned phenol formaldehyde foam feed liquid, blowing agent provides while foaming for feed liquidThe foam of good stability and cell size homogeneous. Based on the foamable phenolic aldehyde of 100 weight portionResin, foaming agent consumption is 5～9 weight portions, if the consumption of blowing agent is lower than 5 weightPart, can cause foaming degree inadequate because foaming agent consumption is not enough, otherwise, ifThe consumption of blowing agent, can be due to the excessive gained that causes of foaming dosage higher than 9 weight portionsIn foam, abscess is excessive, causes gained to cover sand foam board quality badness.
In the preparation of above-mentioned phenol formaldehyde foam feed liquid, nertralizer not only further reduces canThe remaining acidity of the phenolic resins of foaming, and can also improve the anti-of phenol formaldehyde foam layerFire performance, meanwhile, can also absorb the moisture in expandable resin, thus the feed liquid of makingTemperature Distribution when foamable is more even, foaming and rear curing more balanced. Based onThe 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, remaining acid in being difficult to and in foam material liquidComposition, the acidity of gained foam is strong, and corrosivity is strong, thus the potential safety hazard of existence is anti-It, if nertralizer consumption is higher than 45 weight portions, due to the excessive gained that makes of its consumptionThe quality badness of sand clad can composite phenol formaldehyde foam heat-insulating board.
In the preparation of above-mentioned phenol formaldehyde foam feed liquid, carbon black is Powdered, and particle is thin,Specific area is large, and the thermal conductive network forming in feed liquid contributes to feed liquid solid at foamableWhen change, heat conduction is carried out in feed liquid inside, dwindles the temperature difference, while avoiding foaming due to partExcess Temperature causes abscess to break and coalescence, produces large abscess, thereby affects phenolic aldehyde bubbleThe heat insulating ability of foam layer and mechanical strength. 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,Good heat conduction effect, makes after feed liquid heating, Temperature Distribution equilibrium, thus make foamStable homogeneous, does not break. If parts by weight are lower than 0.2 part, due to consumption very little, leadThermal effect is bad, if umber is greater than 3 parts, again can be too much because of consumption, and affect phenolic aldehyde bubbleThe combination property of foam layer, as heat insulating ability, mechanical strength.
In the preparation of above-mentioned phenol formaldehyde foam feed liquid, based on the foamable phenol of 100 weight portionUrea formaldehyde, hardener dose is 10～25 weight portions. If hardener dose is lower than 10Weight portion, because the too low meeting of hardener dose causes foam curing degree inadequate, otherwise,If hardener dose, higher than 25 weight portions, causes solidifying because hardener dose is too highExcessive velocities, gained covers the quality badness of sand foam board. In addition, curing agent also risesTo the rear curing effect at 45～90 DEG C of catalysed phenolic resin adhesive, make and phenolAldehyde froth bed forms integrated cross-linked network, thereby gives the cohesive force that sand grains is larger.
In a preferred embodiment, curing agent is p-methyl benzenesulfonic acid or to toluene sulphurThe mixture of acid and sulfuric acid, p-methyl benzenesulfonic acid or p-methyl benzenesulfonic acid mix with sulfuric acidEffect curing after the solidification effect of thing and catalysis is better.
In a preferred embodiment, the surfactant in phenol formaldehyde foam feed liquid is preferred3～4 weight portions, in this weight portion, play best stable foam and make abscessUniform effect, blowing agent is 5～8 weight portions preferably, in this weight portion, canObtain the foam of optimal stability, nertralizer is 10～20 weight portions preferably, in this weightIn part, can obtain acid low phenol formaldehyde foam, reduce body of wall and metal steelframe aroundThe corrosion of structure, thereby the potential safety hazard of avoiding.
In a preferred embodiment, after end liner is laid on mould, be preheated to 30～After 40 DEG C, apply fast phenol formaldehyde foam feed liquid at the non-sand face of planting of end liner, then put intoFoamed solidification in the baking oven of 60～80 DEG C. Mould and end liner are preheated to 30 in advance～40 DEG C, the temperature difference can reduce with the moulding of phenol formaldehyde foam feed liquid foamed solidification time, is conducive toThe heat insulating ability of phenol formaldehyde foam layer, mechanical property.
In a preferred embodiment, lining cloth is nonwoven, glass fabric, braidingOne or more in fiber cloth, lining cloth is as matrix, its resistance to water, wearability andPliability is all better than using paper as matrix, and sand grains is river sand, extra large sand, ore in sand form, artificialOne or more in color sand dye.
According to a further aspect in the invention, foamable phenolic resins is by comprising following stepRapid preparation:
(a) phenol, paraformaldehyde and demineralized water are added in reactor, open stirringAnd condenser pipe, maintaining temperature of charge is 30 DEG C～40 DEG C, wherein, and the use of paraformaldehydeAmount for phenol weight 38%～65%, the consumption of demineralized water be 40% of phenol weight～70%；
(b) in above-mentioned (a), add catalyst, be slowly warming up to 80 DEG C～90 DEG C,Isothermal reaction 2～4h, wherein, the consumption of catalyst is 0.5%～2% of phenol weight;
(c) after isothermal reaction 2～4h, add nertralizer, its consumption is phenol weight1～15%;
(d) vacuumize dehydration after having neutralized, vacuum is-0.08～-0.095MPa,In the time that system viscosity is 2000mPa ﹒ S～9000mPa ﹒ S, cooling discharging; Wherein,
Described catalyst is the one in NaOH, ammoniacal liquor, sodium carbonate, potashOr multiple, barium hydroxide, aluminium hydroxide, hydrogen that described nertralizer is solid granularOne or more in magnesia, magnesia and calcium oxide.
In the preparation of above-mentioned foamable phenolic resins, phenolic resins be by phenol andParaformaldehyde carries out condensation polymerization and prepares. Wherein, paraformaldehyde replaces unskilled laborIndustry formalin carries 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 contracts at phenolic aldehydeClose in polymerization process and be coated by the phenolic resins that is generated, the nertralizer that these are wrapped byParticle can be sent out with phenol formaldehyde foam feed liquid after phenol formaldehyde foam feed liquid is during through foamed solidification mouldingThere is neutralization reaction fast in the acid of retaining after bubble curing molding, thereby consumes phenolic aldehyde bubbleThe acid of retaining in foam feed liquid, therefore above-mentioned foamable phenolic resins is suitable for preparing low acidProperty phenol formaldehyde foam, reduced to metope and and the corrosivity of corollary equipment, thereby subtractFew 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 phenol weight0.5%～2% of amount, 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 tripFrom formaldehyde, reach environmental protection and do not affect the insulation of phenol formaldehyde foam layer and the work of wearabilityWith, described flexibilizer is ethylene glycol, Macrogol 200, polyethylene glycol 500, poly-secondIn glycol 800, polyethylene glycol 1500, PPG 6205, liquid nitrile rubberOne or more, make phenol formaldehyde foam layer pliability good.
In accordance with a further aspect of the present invention, obtain by preparation method provided by the inventionA kind of sand clad can composite phenol formaldehyde foam heat-insulating board, comprise 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 the beginning of spraying in advance aerodux process on lining clothStep is solidified and rear curing rear formation, and lining cloth layer is positioned at phenol formaldehyde foam layer and surperficial sand grains layerBetween, play 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, in order to provideThermal and insulating performance, phenol formaldehyde foam layer thickness should not be lower than 2cm, and concrete thickness canBy phenolic aldehyde in the distance between mould bottom surface and the end face of foaming use and unit areThe amount of application of foam material liquid regulates. In addition the aerodux in lining cloth layer,When spraying, to ensure that adhesive uniform fold lives lining cloth, but be difficult for blocked up, otherwise meetingAffect cohesive force.
In accordance with a further aspect of the present invention, provide a kind of two-sided sand composite phenol formaldehyde foam that coversWarming plate preparation method, comprises the following steps:
(1) pre-spraying aerodux on lining cloth, then plants by gravitational methodSand forms surperficial sand grains layer, and the lining cloth that forms surperficial sand grains layer is added at 90～130 DEG CHeat makes, after aerodux primary solidification, to make end liner for 5～60 minutes;
(2) end liner good primary solidification is faced down to plant sand, the non-sand of planting is supineMode is laid on mould, applies phenol formaldehyde foam feed liquid, then at phenol at the non-sand face of plantingAldehyde foam material liquid top adds the end liner that lid layer primary solidification is good, finally at 45～90 DEG CLower heating makes phenol formaldehyde foam feed liquid foamed solidification;
(3) form after phenol formaldehyde foam layer cooling frame at phenol formaldehyde foam feed liquid foamed solidificationTool is to room temperature, and the then demoulding, can obtain the two-sided sand composite phenol formaldehyde foam heat-insulating board that covers.
At described two-sided covering in sand composite phenol formaldehyde foam heat-insulating board, the two-sided sand that covers of warming plateFor thermal and insulating performance is provided, phenol formaldehyde foam layer thickness should not be lower than 2cm, specificallyDistance and unit are when thickness can pass through foaming between mould bottom surface and end faceThe amount of application of upper foamable phenolic resins regulates.
Embodiment
Further describe the present invention by instantiation below. But these examples onlyBe exemplary, protection scope of the present invention do not formed to any restriction.
In following embodiment and comparative example:
Paraformaldehyde (Paraformaldehyde): CASNO.:30525-89-4, JiSouth century sensible Chemical Co., Ltd..
Embodiment 1
(1) get 0.5 square metre of the nonwoven that every square metre of quality is 60g, gotOn nonwoven, evenly spray urea formaldehyde adhesive, then at spraying aeroduxLining cloth on cover that to spread average diameter be the river sand 400g of 0.5 millimeter, make river sand uniform foldAdhesive forms surperficial sand grains layer, and be then placed in 110 DEG C of baking ovens and heat 20 minutes,To end liner;
(2) above-mentioned end liner is faced down to plant sand, the non-supine mode of sand of planting tilesBe the mold bottom of 5 centimetres being laid in inner chamber thickness, by mould and die preheating to 40 DEG C,The non-sand face of planting applies phenol formaldehyde foam feed liquid fast, and then at 80 DEG C, heating makes phenolic aldehyde bubbleFoam feed liquid foamed solidification forms phenol formaldehyde foam layer;
(3) form after phenol formaldehyde foam layer at phenol formaldehyde foam feed liquid foamed solidification, take out mouldTool is cooled to room temperature, and the then demoulding obtains sand clad can composite phenol formaldehyde foam heat-insulating board;
Wherein, aerodux is by the foamable phenolic resins of 65g and 1.5g polyoxyChange ethene and evenly mix and make,
Wherein, phenol formaldehyde foam feed liquid is by the foamable phenolic resins of 200g, 6g Tween-80,20g aluminum hydroxide particles, 1g carbon black N339 joins in reactor together with 10g pentaneStir 5min, then add 22g p-methyl benzenesulfonic acid rapid stirring together, mix system,
Wherein, foamable phenolic resins by 1200g phenol, 450g paraformaldehyde and500g demineralized water adds in 5L four-hole boiling flask, opens and stirs and condenser pipe, holding temperatureAt 30 DEG C～40 DEG C, then add 6g NaOH, be slowly warming up to 80 DEG C～90 DEG C,Isothermal reaction 4h, adds 12g melamine and 60g aluminium hydroxide, vacuumizes dehydration,Vacuum is at-0.08～-0.095MPa, when system viscosity reaches 2000mPa ﹒ S, coolingDischarging makes.
Embodiment 2
(1) get 0.5 square metre of the glass-fiber-fabric that every square metre of quality is 120g, getNonwoven on even spraying urea formaldehyde adhesive, then at spraying phenolic resin adhesionOn the lining cloth of agent, cover that to spread average diameter be the extra large sand 500g of 0.5 millimeter, extra large sand is evenly coveredLid adhesive forms surperficial sand grains layer, and be then placed in 120 DEG C 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 tilesBe the mold bottom of 10 centimetres being laid in inner chamber thickness, by mould and die preheating to 45 DEG C,Apply fast phenol formaldehyde foam feed liquid at the non-sand face of planting, then at 70 DEG C, heating makes phenolic aldehydeFoam material liquid foamed solidification forms phenol formaldehyde foam layer;
(3) form after phenol formaldehyde foam layer at phenol formaldehyde foam feed liquid foamed solidification, take out mouldTool is cooled to room temperature, and the then demoulding obtains sand clad can composite phenol formaldehyde foam heat-insulating board;Wherein, described aerodux is by the foamable phenolic resins of 70g and 2g polyoxygenatedEthene is evenly mixed to get;
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 adds together with 28g pentaneEnter in reactor and stir 5min, then add 28g sulfuric acid together with 12g p-methyl benzenesulfonic acidRapid stirring, mixes and makes,
Wherein, foamable phenolic resins by 1200g phenol, 690g paraformaldehyde and750g demineralized water adds in 5L four-hole boiling flask, opens and stirs and condenser pipe, holding temperatureAt 30 DEG C～40 DEG C, add 8.5g magnesia, be slowly warming up to 80 DEG C～90 DEG C, perseveranceTemperature reaction 3h, adds 24gPEG-1500 and 150g aluminium hydroxide, vacuumizes dehydration,Vacuum is at-0.08～-0.095MPa, when system viscosity reaches 4000mPa ﹒ S, coolingDischarging makes.
Comparative example
Comparative example 1
Repeat embodiment 1, wherein, aerodux is the foamable phenolic aldehyde of 65gResin.
Comparative example 2
Repeat embodiment 2, wherein, the lining cloth that has surperficial sand grains layer to form is placed in to 140 DEG CIn baking oven, heat 15 minutes.
Comparative example 3
Repeat embodiment 2, wherein, in described phenol formaldehyde foam feed liquid, do not add carbon blackN220。
Comparative example 4
Repeat embodiment 2, wherein, the addition of carbon black N220 in described phenol formaldehyde foamFor 13g.
Test example
End liner bending property is measured
By gained end liner taking plant the outside mode of layer of sand at diameter on the cylinder of 10cmReel 2 layers, then take off in the non-outside mode of layer of sand of planting and again on same cylinder, roll upAround 2 layers, complete the circulation of a positive and negative coiling, observation lining after the circulation of carrying out reeling for 5 timesCloth configuration of surface.
By embodiment 1, embodiment 2, in comparative example 1 and comparative example 2, the end liner of gained dividesDo not do bending property and measure, result is as shown in table 1:
Table 1
The performance test of phenolic foam heat insulation plate
According to being incubated in the each embodiment of GB/T20974-2007 standard test and comparative examplePlate density, compressive strength, bend fracture power and water absorption rate, result is as shown in table 2:
Table 2
In conjunction with detailed description of the invention and exemplary example, the present invention is carried out in detail aboveIllustrate, but these explanations can not be interpreted as limitation of the present invention. This area skillArt personnel understand, in the situation that not departing from spirit and scope of the invention, and can be to thisInvention technical scheme and embodiment thereof carry out multiple replacement of equal value, modify or improve,These all fall within the scope of the present invention. Protection scope of the present invention is wanted with appended rightAsk and be as the criterion.
Claims (11)
1. a preparation method for sand clad can composite phenol formaldehyde foam heat-insulating board, its feature existsIn, the method comprises the following steps:
(1) pre-spraying aerodux on lining cloth, then by gravitational method in advanceThe lining cloth uppper sand embedding of spraying aerodux forms surperficial sand grains layer, will form surfaceThe lining cloth of sand grains layer heats at 90～130 DEG C makes aerodux preliminary in 5～60 minutesAfter solidifying, make end liner;
(2) end liner good primary solidification faced down to plant sand, non-ly plant the supine side of sandFormula is laid on mould, applies phenol formaldehyde foam feed liquid, then at 45～90 DEG C at the non-sand face of plantingLower heating makes phenol formaldehyde foam feed liquid foamed solidification form phenol formaldehyde foam layer, at foamed solidificationMeanwhile, the aerodux in end liner is further cross-linked and carries out rear solidifying;
(3) form after phenol formaldehyde foam layer cooling die at phenol formaldehyde foam feed liquid foamed solidificationTo room temperature, the then demoulding, can obtain described sand clad can composite phenol formaldehyde foam heat-insulating board;
Wherein, described aerodux is mixed by the composition that comprises following weight proportionClose even preparation:
100 parts, foamable phenolic resins,
2～6 parts of polyethylene glycol oxides,
Wherein, described phenol formaldehyde foam feed liquid is to be mixed by the composition that comprises following weight proportionEvenly preparation:
Wherein, described surfactant for be selected from Tween-40, Tween-80, AK8812,One or more in L5440 and polyethylene glycol oxide; Described blowing agent be benzinum, pentane,One or more in pentamethylene, n-hexane and carrene; Described nertralizer is solidIn granular barium hydroxide, aluminium hydroxide, magnesium hydroxide, magnesia and calcium oxideOne or more; Described carbon black is N220, N234, N326, N330, N339, N375In one or more; Described curing agent is one or more in inorganic acid and organic acid.
2. a kind of sand clad can composite phenol formaldehyde foam heat-insulating board according to claim 1Preparation method, it is characterized in that the preferred p-methyl benzenesulfonic acid of described curing agent or to firstThe mixture of benzene sulfonic acid and sulfuric acid.
3. a kind of sand clad can composite phenol formaldehyde foam heat-insulating board according to claim 1Preparation method, it is characterized in that, described surfactant is 3～4 weight portions preferably, foamingAgent is 5～8 weight portions preferably, and nertralizer is 10～20 weight portions preferably.
4. a kind of sand clad can composite phenol formaldehyde foam heat-insulating board according to claim 1Preparation method, it is characterized in that, in step (2), end liner is laid on mouldAfter, be preheated to after 30～40 DEG C, apply fast phenol formaldehyde foam material at the non-sand face of planting of end linerLiquid, then puts into the baking oven foamed solidification of 60～80 DEG C.
5. a kind of sand clad can composite phenol formaldehyde foam heat-insulating board according to claim 1Preparation method, it is characterized in that, described lining cloth is nonwoven, glass fabric, volumeOne or more in textured fiber cloth, the sand grains in described surperficial sand grains layer is river sand, seaOne or more in sand, ore in sand form, artificially colored color sand.
6. a kind of sand clad can composite phenol formaldehyde foam heat-insulating board according to claim 1Preparation method, it is characterized in that, foamable phenolic resins is by comprising the following steps systemStandby:
(a) phenol, paraformaldehyde and demineralized water are added in reactor, open stir andCondenser pipe, maintaining temperature of charge is 30 DEG C～40 DEG C, wherein, the consumption of paraformaldehyde is38%～65% of phenol weight, the consumption of demineralized water is 40%～70% of phenol weight;
(b) in above-mentioned (a), add catalyst, be slowly warming up to 80 DEG C～90 DEG C,Isothermal reaction 2～4h, wherein, the consumption of catalyst is 0.5%～2% of phenol weight;
(c) after isothermal reaction 2～4h, add nertralizer, its consumption is phenol weight1～15％；
(d) vacuumize dehydration after having neutralized, vacuum is-0.08～-0.095MPa,In the time that system viscosity is 2000mPa ﹒ s～9000mPa ﹒ s, cooling discharging;
Wherein, described catalyst is in NaOH, ammoniacal liquor, sodium carbonate, potashOne or more, barium hydroxide that described nertralizer is solid granular, aluminium hydroxide,One or more in magnesium hydroxide, magnesia and calcium oxide.
7. a kind of sand clad can composite phenol formaldehyde foam heat-insulating board according to claim 1Preparation method, it is characterized in that, described inorganic acid is sulfuric acid, hydrochloric acid, phosphoric acid and nitreAcid, described organic acid is formic acid, oxalic acid, p-methyl benzenesulfonic acid, xylene monosulfonic acid, methylSulfonic acid and DBSA.
8. a kind of sand clad can composite phenol formaldehyde foam heat-insulating board according to claim 6Preparation method, it is characterized in that, in the preparation of foamable phenolic resins, addingWhen entering nertralizer, add formaldehyde catching agent or/and flexibilizer, wherein, described formaldehydeThe consumption of agent for capturing is 0.5%～2% of phenol weight, and the consumption of flexibilizer is phenol weight0.3%～4%.
9. a kind of sand clad can composite phenol formaldehyde foam heat-insulating board according to claim 8Preparation method, it is characterized in that, described formaldehyde catching agent is in urea, melamineOne or more, described flexibilizer be ethylene glycol, Macrogol 200, polyethylene glycol 500,In polyethylene glycol 800, polyethylene glycol 1500, PPG 6205, liquid nitrile rubberOne or more.
10. a kind of sand clad can composite phenol formaldehyde foam heat-insulating board according to claim 1Preparation method, it 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 is preliminary by pre-spraying aerodux process on lining clothSolidify and rear solidify after form, lining cloth layer between phenol formaldehyde foam layer and surperficial sand grains layer,Play the effect of bonding phenol formaldehyde foam layer and surperficial sand grains layer.
11. 1 kinds of two-sided sand composite phenol formaldehyde foam heat-insulating board preparation methods of covering, its feature existsIn, comprise the following steps:
(1) pre-spraying aerodux on lining cloth, then plants sand by gravitational methodForm surperficial sand grains layer, the lining cloth that forms surperficial sand grains layer is heated at 90～130 DEG CWithin 5～60 minutes, make, after aerodux primary solidification, to make end liner;
(2) end liner good primary solidification faced down to plant sand, non-ly plant the supine side of sandFormula is laid on mould, applies phenol formaldehyde foam feed liquid at the non-sand face of planting, and then steeps at phenolic aldehydeFoam feed liquid top adds the end liner that lid layer primary solidification is good, finally at 45～90 DEG C, heats and makesPhenol formaldehyde foam feed liquid foamed solidification;
(3) form after phenol formaldehyde foam layer cooling die at phenol formaldehyde foam feed liquid foamed solidificationTo room temperature, the then demoulding, can obtain the two-sided sand composite phenol formaldehyde foam heat-insulating board that covers.
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