CN101838116A - Hydrophobic granule and preparation method thereof, and waterproof breathable structure and forming method thereof - Google Patents

Hydrophobic granule and preparation method thereof, and waterproof breathable structure and forming method thereof Download PDF

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Publication number
CN101838116A
CN101838116A CN200910203463A CN200910203463A CN101838116A CN 101838116 A CN101838116 A CN 101838116A CN 200910203463 A CN200910203463 A CN 200910203463A CN 200910203463 A CN200910203463 A CN 200910203463A CN 101838116 A CN101838116 A CN 101838116A
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resin
epoxy
hydrophobic
modified epoxy
hydrophobic granule
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CN101838116B (en
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秦升益
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BEIJING RENCHUANG TECHNOLOGY DEVELOPMENT Co.,Ltd.
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Beijing Rechsand Science and Technology Group Co Ltd
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Priority to CN200910203463.7A priority Critical patent/CN101838116B/en
Priority to PCT/CN2010/073011 priority patent/WO2010133174A1/en
Priority to CN2010800122136A priority patent/CN102388114A/en
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K17/00—Soil-conditioning materials or soil-stabilising materials
    • C09K17/14—Soil-conditioning materials or soil-stabilising materials containing organic compounds only
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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    • C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B18/02—Agglomerated materials, e.g. artificial aggregates
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    • C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
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    • C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
    • C04B20/02—Treatment
    • C04B20/04—Heat treatment
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    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
    • C04B20/10—Coating or impregnating
    • C04B20/1018—Coating or impregnating with organic materials
    • C04B20/1029—Macromolecular compounds
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    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
    • C04B20/10—Coating or impregnating
    • C04B20/1051—Organo-metallic compounds; Organo-silicon compounds, e.g. bentone
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    • C04B30/00—Compositions for artificial stone, not containing binders
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    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/0045—Polymers chosen for their physico-chemical characteristics
    • C04B2103/0052—Hydrophobic polymers
    • C—CHEMISTRY; METALLURGY
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    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/60—Agents for protection against chemical, physical or biological attack
    • C04B2103/65—Water proofers or repellants
    • C—CHEMISTRY; METALLURGY
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    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00241—Physical properties of the materials not provided for elsewhere in C04B2111/00
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    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
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    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
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    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
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    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/0075—Uses not provided for elsewhere in C04B2111/00 for road construction
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    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/20—Resistance against chemical, physical or biological attack
    • C04B2111/27—Water resistance, i.e. waterproof or water-repellent materials
    • 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
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
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    • Y02W30/91—Use of waste materials as fillers for mortars or concrete

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Abstract

The invention relates to a hydrophobic granule and a preparation method thereof, and a waterproof breathable structure and a forming method thereof. The hydrophobic granule comprises aggregate and a hydrophobic resin film coated on the aggregate, wherein the aggregate size is 6-300 meshes, and the hydrophobic resin film is made of one or a plurality of hydrophobic epoxy resin, bakelite, polyurethane resin and silicone resin, and coated on the aggregate. The preparation method of the hydrophobic granule comprises the following steps: heating the aggregate to 50-400 DEG C; adding the hydrophobic resin, evenly stirring so that a film is coated on the aggregate surface; and cooling, crushing and screening to obtain the hydrophobic granules. The hydrophobic granule can be widely used as a waterproof breathable layer in desert planting, lake bottom seepage-proofing, river course seepage-proofing, landscape water system bottom seepage-proofing, and has favorable waterproof and breathable properties.

Description

Hydrophobic granule, its preparation method, waterproof and breathable structure and forming method thereof
Technical field
The present invention relates to impervious material, relate in particular to hydrophobic granule, its preparation method and waterproof and breathable structure and forming method thereof.
Background technology
Good, the ageing inadequately weak point of impervious material cost height, anti-seepage effect in the prior art, and often accomplish that antiseepage just causes product airtight, when being used in each field, impervious material produces some side effects, as the antiseepage at the bottom of the landscape lake, in order to keep the lake water water yield, anti-sealing is seeped into underground additional underground water, scheme commonly used in the prior art has: scheme 1: add water-proof material at lakebed with concrete and do waterproof, but cost is higher, and it is airtight, destroyed the geobenthos growth, so its application has very big limitation.Scheme 2: at lakebed layer overlay waterproof membrane, but this waterproof membrane is airtight, has also destroyed the geobenthos growth, has destroyed the ecotope of geobenthos, still can't generally promote.
Chinese patent (application number: 200720103642.X) disclose a kind of concrete for hydraulic structure dam thermal-insulating leakage-resistant composition board, comprise warming plate and composite geo-membrane that thermal insulation material is made, this film comprises the two-sided composite structure of two cloth, one film of geomembrane that water-proof material is made and two sides hot pressing non-woven fabrics.Wherein, this geomembrane is a plastic film, and the layer of surface of geomembrane is coated with the interfacial agents figure layer of a polymer materials, and this interfacial agents figure layer is the polymer emulsion coating.This technical scheme is to realize antiseepage by fluid-tight plastic material, yet the plastics ventilation property is very poor, and is ventilative when can't realize waterproof.
Summary of the invention
Technical problem to be solved by this invention is to propose a kind of hydrophobic granule, its preparation method, waterproof and breathable structure and forming method thereof, and it is bad to be limited in the technology impervious material anti-seepage effect with solution, the problem of ventilation property difference.
For achieving the above object, the present invention proposes a kind of hydrophobic granule, and this hydrophobic granule comprises aggregate and coats the hydrophobic resin film of aggregate.
Wherein, this hydrophobic resin film forms overlay film in one or more particless of aggregates surface.
Wherein, described aggregate is one or more in quartz sand, slag, haydite or the glass microballon, and its particle diameter is the 6-300 order, is preferably the 100-200 order.
Wherein, the quality of described hydrophobic resin film accounts for the 1-8% of aggregate quality.
Wherein, described hydrophobic resin film is by one or more films that form in hydrophobicity Resins, epoxy, resol, urethane resin and the silicone resin.
Preferably, described hydrophobicity Resins, epoxy is the glycidyl ether based epoxy resin, the glycidyl ester based epoxy resin, the Racemic glycidol amine epoxy resin, line style aliphatic category Resins, epoxy, alicyclic based epoxy resin, polysulfide-rubber-modified epoxy, the polyamide resin modified epoxy, polyvinyl alcohol uncle butyraldehyde modified epoxy, acrylonitrile butadiene rubber modified epoxy resin, phenolic resin modified Resins, epoxy, the vibrin modified epoxy, urine aldehyde melamine resin modified epoxy, the furfuryl resin modified epoxy, the ethenoid resin modified epoxy, in isocyanate modified epoxy resin or the silicone resin modified epoxy one or more; Described hydrophobicity resol is one or more in dimethylbenzene modified phenolic resins, epoxy resin modification resol or the organic silicon modified phenolic resin.
And adding in the described hydrophobic resin film has solidifying agent, adds different solidifying agent for different resins, wherein:
For the glycidyl ether based epoxy resin, the glycidyl ester based epoxy resin, the Racemic glycidol amine epoxy resin, line style aliphatic category Resins, epoxy, alicyclic based epoxy resin, polysulfide-rubber-modified epoxy, the polyamide resin modified epoxy, polyvinyl alcohol uncle butyraldehyde modified epoxy, acrylonitrile butadiene rubber modified epoxy resin, phenolic resin modified Resins, epoxy, the vibrin modified epoxy, urine aldehyde melamine resin modified epoxy, the furfuryl resin modified epoxy, the ethenoid resin modified epoxy, isocyanate modified epoxy resin or silicone resin modified epoxy, the solidifying agent that is added is an aliphatic amide, aliphatic cyclic amine, aromatic amine, polymeric amide, acid anhydrides, in the tertiary amine any or several;
For dimethylbenzene modified phenolic resins, epoxy resin modification resol or organic silicon modified phenolic resin, the solidifying agent that is added is a hexamethylenetetramine;
Solidifying agent for silicone resin is dibutyl tin dilaurate or N, N, N ', any in N ' the tetramethyl-guanidinesalt or several;
For the hydrophobicity urethane resin, its solidifying agent is the affixture of TDI and TMP, the tripolymer of the prepolymer of TDI and hydroxyl component and the agent of single-component moisture solidification, TDI.
For unsaturated polyester, the solidifying agent that is added during normal temperature is ketone peroxide and cobalt naphthenate; The solidifying agent that is added during heating is one or more in peroxidized t-butyl perbenzoate, peroxy dicarbonate, dialkyl peroxide, the own ester of peroxidation acid uncle and the bis peroxy dicarbonate.
In addition, for achieving the above object, the present invention also proposes a kind of preparation method of hydrophobic granule, and this method comprises the steps:
Step 1: aggregate is heated to 50-400 ℃;
Step 2: add hydrophobic resin, stir, make it at the aggregate surface overlay film;
Step 3: obtain hydrophobic granule after cooling, fragmentation, the screening.
Wherein, Heating temperature is 100-240 ℃ in the described step 1.
Preferably, the add-on of hydrophobic resin accounts for the 1-8% of aggregate quality in the described step 2.
Preferably, described aggregate is a quartz sand, slag, and haydite, any in the glass microballon, its particle diameter are the 6-300 order.
Wherein, described hydrophobic resin is one or more in hydrophobicity Resins, epoxy, resol, urethane resin, the silicone resin.
Preferably, described hydrophobicity Resins, epoxy is the glycidyl ether based epoxy resin, the glycidyl ester based epoxy resin, the Racemic glycidol amine epoxy resin, line style aliphatic category Resins, epoxy, alicyclic based epoxy resin, polysulfide-rubber-modified epoxy, the polyamide resin modified epoxy, polyvinyl alcohol uncle butyraldehyde modified epoxy, acrylonitrile butadiene rubber modified epoxy resin, phenolic resin modified Resins, epoxy, the vibrin modified epoxy, urine aldehyde melamine resin modified epoxy, the furfuryl resin modified epoxy, the ethenoid resin modified epoxy, in isocyanate modified epoxy resin or the silicone resin modified epoxy one or more; Described hydrophobicity resol is one or more in dimethylbenzene modified phenolic resins, epoxy resin modification resol, the organic silicon modified phenolic resin.
Wherein, in step 2, also comprise the step that adds solidifying agent.
And for achieving the above object, the present invention also proposes a kind of waterproof and breathable structure, comprises a waterproof ventilative layer, and this waterproof ventilative layer is to lay the hydrophobic granule layer that forms by above-mentioned hydrophobic granule.
Wherein, this hydrophobic granule layer below is a basic unit.
Wherein, the plantation hole layer of this basic unit in desert, seabeach, barren beach or soil, forming, this hydrophobic granule layer top is the plantation soil layer.
Wherein, this basic unit is water-bed stratum, and this hydrophobic granule layer top is the water body layer.
And for achieving the above object, the present invention also proposes a kind of method that generates waterproof and breathable structure, and this waterproof and breathable structure comprises a waterproof ventilative layer, and this waterproof ventilative layer is laid by above-mentioned hydrophobic granule and formed.
Wherein, described waterproof ventilative layer is layed in basic unit top.
Wherein, the plantation hole layer of described basic unit in desert, seabeach, barren beach or soil, forming, this hydrophobic granule layer top is the plantation soil layer.
Wherein, this basic unit is water-bed stratum, and this hydrophobic granule layer top is the water body layer.
Compared with prior art, the invention has the beneficial effects as follows:
1, hydrophobic granule of the present invention has excellent hydrophobic property, and this hydrophobic granule has good water tolerance, and hydrophobic timeliness is long, and weathering resistance is strong, has good social benefit and economic benefit;
2, because hydrophobic granule of the present invention does not have any murder by poisoning, therefore safe and environmentally friendly, have good environmental benefit;
3, the bed course that forms with this hydrophobic granule, have excellent waterproof, air permeable effect, can be widely used in using as breathable water repellant layer in lakebed, bottom, river, desert planting, the waterproofing work, therefore can protect water-bed ecotope well, be beneficial to biological growth;
4, construction is easy, cost is low, so cost is low, has good economic benefits;
5, good fluidity, survivability are strong, and abnormity and irregular surface effect are better.
Embodiment
The present invention proposes a kind of hydrophobic granule, this hydrophobic granule comprises aggregate and coats the hydrophobic resin film of aggregate.Wherein, this hydrophobic resin film forms overlay film in one or more particless of aggregates surface.
Particularly, described aggregate is preferably one or more in quartz sand, slag, haydite or the glass microballon, and its particle diameter is preferably 6～300 orders, is more preferred from 100～200 orders.And in described hydrophobic granule, the quality of described hydrophobic resin film accounts for 1～8% of aggregate quality.Wherein, described hydrophobic resin film is by one or more films that form in hydrophobicity Resins, epoxy, hydrophobicity resol, hydrophobicity urethane resin and the silicone resin.Described hydrophobicity Resins, epoxy is preferably the glycidyl ether based epoxy resin, the glycidyl ester based epoxy resin, the Racemic glycidol amine epoxy resin, line style aliphatic category Resins, epoxy, alicyclic based epoxy resin, polysulfide-rubber-modified epoxy, the polyamide resin modified epoxy, polyvinyl alcohol uncle butyraldehyde modified epoxy, acrylonitrile butadiene rubber modified epoxy resin, phenolic resin modified Resins, epoxy, the vibrin modified epoxy, urine aldehyde melamine resin modified epoxy, the furfuryl resin modified epoxy, the ethenoid resin modified epoxy, in isocyanate modified epoxy resin or the silicone resin modified epoxy one or more; Described hydrophobicity resol is preferably one or more in dimethylbenzene modified phenolic resins, epoxy resin modification resol or the organic silicon modified phenolic resin.
And hydrophobic resin as previously discussed can obtain by following method modification, and concrete method of modifying is:
With Resins, epoxy, as Tetra hydro Phthalic anhydride or maleic anhydride, with oil-soluble monomer copolymerization, described oil-soluble monomer is: alkyl acrylate, alkyl methacrylate, any in ethylacrylic acid, vinyl acetate, allyl acetate, sodium vinyl sulfonate, methylvinylether, methallyl ether, dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate, vinylformic acid dimethylamino propyl ester, vinylformic acid diethylin propyl ester, vinylformic acid dimethylamino butyl ester, dimethylaminoethyl methacrylate, the diethylaminoethyl methacrylate.
Perhaps, also the Resins, epoxy graft modification can be formed graftomer; With the hydrophilic radical of Resins, epoxy, as hydroxyl, react with hydrophobic function monomer, it is connect; Hydrophobic function monomer is: phenyl aldehyde, alkylbenzene formaldehyde (a big class) utilizes the reaction of hydroxyl and aldehyde radical.
Perhaps, also Resins, epoxy can be carried out substitution reaction, under the catalyzed reaction of illumination, participate in substitution reaction, halogen be received above the Resins, epoxy, to improve hydrophobic performance with chlorine.
In addition, can add in the described hydrophobic resin film has solidifying agent, and, add different solidifying agent for different resins, wherein, the selection of solidifying agent is specific as follows:
For the glycidyl ether based epoxy resin, the glycidyl ester based epoxy resin, the Racemic glycidol amine epoxy resin, line style aliphatic category Resins, epoxy, alicyclic based epoxy resin, polysulfide-rubber-modified epoxy, the polyamide resin modified epoxy, polyvinyl alcohol uncle butyraldehyde modified epoxy, acrylonitrile butadiene rubber modified epoxy resin, phenolic resin modified Resins, epoxy, the vibrin modified epoxy, urine aldehyde melamine resin modified epoxy, the furfuryl resin modified epoxy, the ethenoid resin modified epoxy, isocyanate modified epoxy resin or silicone resin modified epoxy, preferable solidifying agent are aliphatic amide, aliphatic cyclic amine, aromatic amine, polymeric amide, acid anhydrides, in the tertiary amine any or several;
For dimethylbenzene modified phenolic resins, epoxy resin modification resol or organic silicon modified phenolic resin, preferable solidifying agent is a hexamethylenetetramine;
For silicone resin, preferable solidifying agent is dibutyl tin dilaurate or N, N, N ', any in N ' the tetramethyl-guanidinesalt or several;
For the hydrophobicity urethane resin, its solidifying agent is the affixture of TDI and TMP, the tripolymer of the prepolymer of TDI and hydroxyl component and the agent of single-component moisture solidification, TDI.
For unsaturated polyester (polymkeric substance of terephthalic acid and ethylene glycol), the solidifying agent that is added during normal temperature is ketone peroxide and cobalt naphthenate; The solidifying agent that is added during heating is one or more in peroxidized t-butyl perbenzoate, peroxy dicarbonate, dialkyl peroxide, the own ester of peroxidation acid uncle and the bis peroxy dicarbonate.
In addition, the present invention also provides a kind of preparation method of above-mentioned hydrophobic granule, and this method comprises the steps:
Step 1: aggregate is heated to 50～400 ℃;
Step 2: add hydrophobic resin, stir, make it at the aggregate surface overlay film;
Step 3: obtain hydrophobic granule after cooling, fragmentation, the screening.
Wherein, in the step 1, the preferable selection particle diameter of described aggregate is 6～300 purpose quartz sands, slag, haydite, any in the glass microballon, better selection 100～200 purpose quartz sands.And Heating temperature is preferably 100～240 ℃.
The add-on of hydrophobic resin accounts for 1～8% of aggregate quality in the described step 2.And described hydrophobic resin is selected one or more in hydrophobicity Resins, epoxy, resol, urethane resin, the silicone resin.Preferably, described hydrophobicity Resins, epoxy is the glycidyl ether based epoxy resin, the glycidyl ester based epoxy resin, the Racemic glycidol amine epoxy resin, line style aliphatic category Resins, epoxy, alicyclic based epoxy resin, polysulfide-rubber-modified epoxy, the polyamide resin modified epoxy, polyvinyl alcohol uncle butyraldehyde modified epoxy, acrylonitrile butadiene rubber modified epoxy resin, phenolic resin modified Resins, epoxy, the vibrin modified epoxy, urine aldehyde melamine resin modified epoxy, the furfuryl resin modified epoxy, the ethenoid resin modified epoxy, in isocyanate modified epoxy resin or the silicone resin modified epoxy one or more; Described hydrophobicity resol is one or more in dimethylbenzene modified phenolic resins, epoxy resin modification resol, the organic silicon modified phenolic resin.
And above-mentioned hydrophobic resin can obtain by following method modification, and concrete method of modifying is:
With Resins, epoxy, as Tetra hydro Phthalic anhydride or maleic anhydride, with oil-soluble monomer copolymerization, form multipolymer: described oil-soluble monomer is: alkyl acrylate, alkyl methacrylate, ethylacrylic acid, vinyl acetate, allyl acetate, sodium vinyl sulfonate, methylvinylether, methallyl ether, dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate, vinylformic acid dimethylamino propyl ester, vinylformic acid diethylin propyl ester, vinylformic acid dimethylamino butyl ester, dimethylaminoethyl methacrylate, in the diethylaminoethyl methacrylate any.
Perhaps, also the Resins, epoxy graft modification can be formed graftomer; With the hydrophilic radical of Resins, epoxy, as hydroxyl, react with hydrophobic function monomer, it is connect; Hydrophobic function monomer is: phenyl aldehyde, alkylbenzene formaldehyde (a big class) utilizes the reaction of hydroxyl and aldehyde radical.
Perhaps, also Resins, epoxy can be carried out substitution reaction, under the catalyzed reaction of illumination, participate in substitution reaction, halogen be received above the Resins, epoxy, to improve hydrophobic performance with chlorine.
Wherein, can directly add the hydrophobic resin after liquid hydrophobic resin or solvent dissolve, or, spray to aggregate surface the hydrophobic resin atomizing.
In addition, in the overlay film step of step 2, can add different solidifying agent at different resins, preferably, for the glycidyl ether based epoxy resin, the glycidyl ester based epoxy resin, the Racemic glycidol amine epoxy resin, line style aliphatic category Resins, epoxy, alicyclic based epoxy resin, polysulfide-rubber-modified epoxy, the polyamide resin modified epoxy, polyvinyl alcohol uncle butyraldehyde modified epoxy, acrylonitrile butadiene rubber modified epoxy resin, phenolic resin modified Resins, epoxy, the vibrin modified epoxy, urine aldehyde melamine resin modified epoxy, the furfuryl resin modified epoxy, the ethenoid resin modified epoxy, isocyanate modified epoxy resin or silicone resin modified epoxy add the solidifying agent aliphatic amide, aliphatic cyclic amine, aromatic amine, polymeric amide, acid anhydrides, in the tertiary amine any or several;
For dimethylbenzene modified phenolic resins, epoxy resin modification resol or organic silicon modified phenolic resin, add the solidifying agent hexamethylenetetramine;
For the hydrophobicity urethane resin, its solidifying agent is the affixture of TDI and TMP, the tripolymer of the prepolymer of TDI and hydroxyl component and the agent of single-component moisture solidification, TDI.
For silicone resin, add solidifying agent dibutyl tin dilaurate or N, N, N ', any in N ' the tetramethyl-guanidinesalt or several;
For unsaturated polyester, add solidifying agent ketone peroxide and cobalt naphthenate during normal temperature; During heating in adding solidifying agent peroxidized t-butyl perbenzoate, peroxy dicarbonate, dialkyl peroxide, the own ester of peroxidation acid uncle and the bis peroxy dicarbonate one or more.
In addition, before step 1, can soak aggregate with the butyrous material earlier, as hexane, 120# solvent oil, rape seed oil, peanut oil, Oleum Helianthi, soya-bean oil, salad wet goods.
Below for the preferred embodiment of hydrophobic granule of the present invention:
Embodiment 1:
Select 6 purpose quartz sand particles, 100 grams, be heated to 50 ℃, afterwards, add liquid polyethylene alcohol uncle butyraldehyde modified epoxy 6 grams, fully stir, add polyamide curing agent 1 gram again, stir, make Resins, epoxy at the quartz sand particle surface coating; Yet, after cooling, obtain hydrophobic granule after fragmentation, the screening.
Embodiment 2:
Select 300 purpose quartz sand particles, 200 grams, be heated to 400 ℃, add polyamide resin modified epoxy 14 grams, fully stir, and add aliphatic cyclic amine, make the quartz sand particle surface form the silicone resin overlay film, afterwards, cooling, fragmentation, screening obtain hydrophobic granule.
Embodiment 3:
Select 100 purpose quartz sand particles, 100 grams, be heated to 100 ℃, afterwards, add dimethylbenzene modified phenolic resins 4 grams, add the hexamethylenetetramine solidifying agent simultaneously, fully stir, make that the resol and the solidifying agent that are added are even respectively, and at the quartz sand particle surface coating; Then, obtain hydrophobic granule after cooling, fragmentation, the screening.
Embodiment 4:
Select 200 order quartz sand particles, 200 grams, be heated to 240 ℃, then, with 10 gram silicone resin atomizings, spray to the quartz sand particle surface, and add the solidifying agent dibutyl tin dilaurate, fully stir, make the quartz sand particle surface form the silicone resin overlay film, afterwards, cooling, fragmentation, screening obtain hydrophobic granule.
Embodiment 5
Hydrophobic granule as previously discussed, described aggregate are quartz sand, and particle diameter is 6 orders, the film that described hydrophobic resin film forms when being the described aggregate of any resin-coated in hydrophobicity Resins, epoxy, resol, urethane resin, the silicone resin film.
Embodiment 6
Hydrophobic granule as previously discussed, described aggregate are quartz sand, and particle diameter is 300 orders, the film that described hydrophobic resin film forms when being the described aggregate of any resin-coated in hydrophobicity Resins, epoxy, resol, urethane resin, the silicone resin film.
Embodiment 7
Hydrophobic granule as previously discussed, described aggregate are quartz sand, and particle diameter is 150 orders, the film that described hydrophobic resin film forms when being the described aggregate of any resin-coated in hydrophobicity Resins, epoxy, resol, urethane resin, the silicone resin film.
Embodiment 8
Hydrophobic granule as previously discussed, the particle diameter of described quartz sand are 100 orders; Hydrophobicity Resins, epoxy is glycidyl ether based epoxy resin, glycidyl ester based epoxy resin, Racemic glycidol amine epoxy resin, line style aliphatic category Resins, epoxy, alicyclic based epoxy resin, or in the polysulfide-rubber-modified epoxy, polyamide resin modified epoxy, polyvinyl alcohol uncle butyraldehyde modified epoxy any; Described hydrophobicity resol is any in dimethylbenzene modified phenolic resins, epoxy resin modification resol, the organic silicon modified phenolic resin.
Embodiment 9
Hydrophobic granule as previously discussed, the particle diameter of described quartz sand are 200 orders; Hydrophobicity Resins, epoxy is glycidyl ether based epoxy resin, glycidyl ester based epoxy resin, Racemic glycidol amine epoxy resin, line style aliphatic category Resins, epoxy, alicyclic based epoxy resin, or in the polysulfide-rubber-modified epoxy, polyamide resin modified epoxy, polyvinyl alcohol uncle butyraldehyde modified epoxy any; Described hydrophobicity resol is any in dimethylbenzene modified phenolic resins, epoxy resin modification resol, the organic silicon modified phenolic resin.
Embodiment 10
Hydrophobic granule as previously discussed, described aggregate are slag, haydite, any in the glass microballon.Its particle diameter is: 6 orders.
Embodiment 11
Hydrophobic granule as previously discussed, described aggregate are slag, haydite, any in the glass microballon.Its particle diameter is: 300 orders.
Embodiment 12
Hydrophobic granule as previously discussed, described aggregate are slag, haydite, any in the glass microballon.Its particle diameter is: 150 orders.
Embodiment 13
A kind of preparation method of hydrophobic granule, the hydrophobic resin after the hydrophobic resin of liquid state or solvent dissolved mixes stirring with aggregate, and adds solidifying agent, obtains hydrophobic granule after broken, the screening.
Embodiment 14
A kind of preparation method of hydrophobic granule with described resin atomizing, sprays to aggregate surface, stirs, and then: heating and adding solidifying agent are cured, and obtain hydrophobic granule after fragmentation, the screening.
Embodiment 15
A kind of preparation method of hydrophobic granule with described resin atomizing, sprays to aggregate surface, stirs, and obtains hydrophobic granule after fragmentation, the screening.
Embodiment 16
The preparation method of hydrophobic granule in the aggregate overlay film process, carries out hydrophobic modified to described resin as previously discussed.
Embodiment 17
The preparation method of hydrophobic granule adds solidifying agent: urotropine after aggregate soaks and takes out after 5 minutes in resol as previously discussed.
Embodiment 18
The preparation method of hydrophobic granule adds solidifying agent: urotropine after aggregate soaks and takes out after 10 minutes in resol as previously discussed.
Embodiment 19
The preparation method of hydrophobic granule as previously discussed, described resin accounts for aggregate quality 4%; Described aggregate is a quartz sand, and particle diameter is 150 orders.
Embodiment 20
The preparation method of hydrophobic granule as previously discussed, described resin accounts for aggregate quality 1%; Described aggregate is a quartz sand, and particle diameter is 300 orders.
Embodiment 21
The preparation method of hydrophobic granule as previously discussed, described resin accounts for aggregate quality 8%; Described aggregate is a quartz sand, and particle diameter is 6 orders.
Embodiment 22
The preparation method of hydrophobic granule as previously discussed, the particle diameter of described quartz sand is 100 orders, the aggregate Heating temperature is 240 ℃.
Embodiment 23
The preparation method of hydrophobic granule as previously discussed, the particle diameter of described quartz sand is 200 orders, the aggregate Heating temperature is 100 ℃.
Embodiment 24
The preparation method of hydrophobic granule as previously discussed, the particle diameter of described quartz sand is 150 orders, the aggregate Heating temperature is 160 ℃.
Embodiment 25
The preparation method of hydrophobic granule as previously discussed, described scoriaceous particle diameter is 100 orders, the aggregate Heating temperature is 240 ℃.
Embodiment 26
The preparation method of hydrophobic granule as previously discussed, the particle diameter of described haydite is 200 orders, the aggregate Heating temperature is 100 ℃.
Embodiment 27
The preparation method of hydrophobic granule as previously discussed, the particle diameter of described glass microballon is 150 orders, the aggregate Heating temperature is 160 ℃.
Embodiment 28
The preparation method of hydrophobic granule as previously discussed, described scoriaceous particle diameter is 200 orders, the aggregate Heating temperature is 240 ℃.
Embodiment 29
The preparation method of hydrophobic granule as previously discussed, the particle diameter of described haydite is 100 orders, the aggregate Heating temperature is 100 ℃.
Embodiment 30
The preparation method of hydrophobic granule as previously discussed, the particle diameter of described glass microballon is 100 orders, the aggregate Heating temperature is 160 ℃.
Below by to the Air permenbility of the hydrophobic granule of embodiment 1～4 gained and the detection of water resistance, the hydrophobic performance and the permeability of hydrophobic granule of the present invention described:
Air permenbility detection side ratio juris is: utilize pressure differential method to test, at normal temperatures, make the sample both sides keep certain gas differential pressure, by measurement sample low-tension side variation of gas pressure, thereby calculate Air permenbility.
Table 1. Air permenbility measured data table
Figure B2009102034637D0000111
The water resistance of hydrophobic granule of the present invention characterizes with main laying height and waterproof height thereof by hydrophobic granule particle diameter, hydrophobic granule layer, wherein, the waterproof height refers to that under the situation of the laying height of determining hydrophobic granule particle diameter and hydrophobic granule layer water begins the critical height that occurs permeating, and, in actual use, needs according to different waterproof height, can highly regulate its waterproof height by changing the laying of hydrophobic granule particle diameter and/or hydrophobic granule, make its waterproof height reach tens down to more than the hundreds of rice, in addition higher.
Table 2 is the experimental data of water resistance of the hydrophobic granule of the embodiment of the invention 1～4: wherein, embodiment 1～4 is under the constant situation of other condition, its grain diameter is changed into data (as 10,50,100,200) in the above table, and its test experience result sees Table 2 in the lump:
Table 2:
Figure B2009102034637D0000121
In addition, the prepared hydrophobic granule of the present invention can be used in different field, as:
Application in the waterproof ventilative layer when desert planting, seabeach plantation, barren beach transformation, ornamencal flower and tree breed.
The application of hydrophobic granule in the waterproof ventilative layer of lakebed antiseepage, river course antiseepage, the bottom antiseepage of view water system.
The application of hydrophobic granule in the engineering waterproofing layer of rainwater recycling, buildings waterproof, flood control installation.
Based on this, the present invention proposes a kind of waterproof and breathable structure, this waterproof and breathable structure comprises a waterproof ventilative layer, this waterproof ventilative layer is to lay the hydrophobic granule layer that forms by hydrophobic granule of the present invention.Wherein, this hydrophobic granule layer below is a basic unit, preferably, the plantation hole layer of this basic unit in desert, seabeach, barren beach or soil, forming, and this hydrophobic granule layer top is for the plantation soil layer, in wherein planting various vegetation; Perhaps, preferably, this basic unit is water-bed stratum, and as the water-bed stratum of lake, river course, landscape water, this hydrophobic granule layer top is corresponding water body layer.
Correspondingly, the present invention proposes the formation method of above-mentioned waterproof and breathable structure, wherein, lay the waterproof ventilative layer that forms this waterproof and breathable structure by hydrophobic granule of the present invention, particularly, described hydrophobic granule is layed in basic unit top forms waterproof ventilative layer, this basic unit can be and excavate the plantation hole layer that forms in desert, seabeach, barren beach or soil, form the plantation soil layer in this waterproof ventilative layer top, in the vegetation of wherein planting the desire plantation.
Perhaps, this basic unit is the water-bed stratum of artificial or natural water such as lake, river course, landscape water, above this stratum, bottom, lay hydrophobic granule, form breathable water repellant layer, this breathable water repellant layer top be corresponding water body, and, can be according to the hydrophobic granule of the different depths employing different-grain diameter of water body, lay the hydrophobic granule layer of different heights, make it have the waterproof height that adapts to the water body requirement.
Concrete Application Example:
1, the application in the plantation plant of hydrophobic granule of the present invention under severe environment such as desert, seabeach and saltings:
In the desert, seabeach and the saline and alkaline excavation tree well that is located in, lay hydrophobic granule in the tree well bottom, carry out plant growing again, can guarantee the rainwater self-restraint near root system of plant, prevent moisture penetration, be diffused into sand bed loss, the material that can prevent the seawater in the stratum such as seabeach, saltings again and be unfavorable for vegetation growth is penetrated near the root system of plant with moisture content.Hydrophobic granule has the high ventilation performance simultaneously, above-mentioned two-layer connection can be helped plant-growth.
2, the application of hydrophobic granule of the present invention in nature, artificial water and water quality keep:
Lay sand bed and metalling at lakebed earlier, lay the hydrophobic granule layer more in the above, can play good anti-seepage effect, water body layer and stratum ground vapour can be connected again, guarantee vegeto-animal life condition in the water: prevent that effectively water body is rotten, water environment degradation, above-mentioned water body is kept ecological balance.
More greatly or easily should be increased sand or rubble protection for flowability by what the external world destroyed waterproof sand.
Compared with prior art, the invention has the beneficial effects as follows:
1, hydrophobic granule of the present invention has excellent hydrophobic property, and this hydrophobic granule has good water tolerance, and hydrophobic timeliness is long, and weathering resistance is strong, has good social benefit and economic benefit;
2, because hydrophobic granule of the present invention does not have any murder by poisoning, therefore safe and environmentally friendly, have good environmental benefit;
3, the bed course that forms with this hydrophobic granule, have excellent waterproof, air permeable effect, can be widely used in using as breathable water repellant layer in lakebed, bottom, river, desert planting, the waterproofing work, therefore can protect water-bed ecotope well, be beneficial to biological growth;
4, construction is easy, cost is low, so cost is low, has good economic benefits;
5, good fluidity, survivability are strong, and abnormity and irregular surface effect are better.
Should be noted that: above embodiment is just in order to do further more detailed description to this invention; it or not the protection domain that is used for limiting this invention; in the scope of spirit that does not break away from this invention and design; those of ordinary skills can be used for various modifications or change, and still belong to the protection domain of this invention.

Claims (24)

1. a hydrophobic granule is characterized in that, this hydrophobic granule comprises aggregate and coats the hydrophobic resin film of aggregate.
2. hydrophobic granule according to claim 1 is characterized in that, this hydrophobic resin film forms overlay film in one or more particless of aggregates surface.
3. hydrophobic granule as claimed in claim 1 is characterized in that, described aggregate is one or more in quartz sand, slag, haydite or the glass microballon, and its particle diameter is the 6-300 order.
4. hydrophobic granule according to claim 1 is characterized in that, the particle diameter of described aggregate is the 100-200 order.
5. hydrophobic granule according to claim 1 is characterized in that, the quality of described hydrophobic resin film accounts for the 1-8% of aggregate quality.
6. as any described hydrophobic granule in the claim 1 to 5, it is characterized in that described hydrophobic resin film is by one or more films that form in hydrophobicity Resins, epoxy, resol, urethane resin and the silicone resin.
7. hydrophobic granule according to claim 6, it is characterized in that described hydrophobicity Resins, epoxy is the glycidyl ether based epoxy resin, the glycidyl ester based epoxy resin, the Racemic glycidol amine epoxy resin, line style aliphatic category Resins, epoxy, alicyclic based epoxy resin, polysulfide-rubber-modified epoxy, the polyamide resin modified epoxy, polyvinyl alcohol uncle butyraldehyde modified epoxy, acrylonitrile butadiene rubber modified epoxy resin, phenolic resin modified Resins, epoxy, the vibrin modified epoxy, urine aldehyde melamine resin modified epoxy, the furfuryl resin modified epoxy, the ethenoid resin modified epoxy, in isocyanate modified epoxy resin or the silicone resin modified epoxy one or more; Described hydrophobicity resol is one or more in dimethylbenzene modified phenolic resins, epoxy resin modification resol or the organic silicon modified phenolic resin.
8. hydrophobic granule according to claim 7 is characterized in that, adding in the described hydrophobic resin film has solidifying agent.
9. hydrophobic granule according to claim 7 is characterized in that, adds different solidifying agent for different resins, wherein:
For the glycidyl ether based epoxy resin, the glycidyl ester based epoxy resin, the Racemic glycidol amine epoxy resin, line style aliphatic category Resins, epoxy, alicyclic based epoxy resin, polysulfide-rubber-modified epoxy, the polyamide resin modified epoxy, polyvinyl alcohol uncle butyraldehyde modified epoxy, acrylonitrile butadiene rubber modified epoxy resin, phenolic resin modified Resins, epoxy, the vibrin modified epoxy, urine aldehyde melamine resin modified epoxy, the furfuryl resin modified epoxy, the ethenoid resin modified epoxy, isocyanate modified epoxy resin or silicone resin modified epoxy, the solidifying agent that is added is an aliphatic amide, aliphatic cyclic amine, aromatic amine, polymeric amide, acid anhydrides, in the tertiary amine any or several;
For dimethylbenzene modified phenolic resins, epoxy resin modification resol or organic silicon modified phenolic resin, the solidifying agent that is added is a hexamethylenetetramine;
Solidifying agent for silicone resin is dibutyl tin dilaurate or N, N, N ', any in N ' the tetramethyl-guanidinesalt or several;
Solidifying agent for the hydrophobicity urethane resin is the affixture of TDI and TMP, the tripolymer of the prepolymer of TDI and hydroxyl component and the agent of single-component moisture solidification, TDI.
10. the preparation method of a hydrophobic granule is characterized in that, this method comprises the steps:
Step 1: aggregate is heated to 50-400 ℃;
Step 2: add hydrophobic resin, stir, make it at the aggregate surface overlay film;
Step 3: obtain hydrophobic granule after cooling, fragmentation, the screening.
11. the preparation method as hydrophobic granule as described in the claim 10 is characterized in that Heating temperature is 100～240 ℃ in the described step 1.
12. the preparation method as hydrophobic granule as described in the claim 10 is characterized in that the add-on of hydrophobic resin accounts for 1～8% of aggregate quality in the described step 2.
13. the preparation method as hydrophobic granule as described in the claim 10 is characterized in that described aggregate is a quartz sand, slag, and haydite, any in the glass microballon, its particle diameter are 6～300 orders.
14. the preparation method of hydrophobic granule as claimed in claim 10 is characterized in that, described hydrophobic resin is one or more in hydrophobicity Resins, epoxy, resol, urethane resin, the silicone resin.
15. the preparation method of hydrophobic granule as claimed in claim 14, it is characterized in that described hydrophobicity Resins, epoxy is the glycidyl ether based epoxy resin, the glycidyl ester based epoxy resin, the Racemic glycidol amine epoxy resin, line style aliphatic category Resins, epoxy, alicyclic based epoxy resin, polysulfide-rubber-modified epoxy, the polyamide resin modified epoxy, polyvinyl alcohol uncle butyraldehyde modified epoxy, acrylonitrile butadiene rubber modified epoxy resin, phenolic resin modified Resins, epoxy, the vibrin modified epoxy, urine aldehyde melamine resin modified epoxy, the furfuryl resin modified epoxy, the ethenoid resin modified epoxy, in isocyanate modified epoxy resin or the silicone resin modified epoxy one or more; Described hydrophobicity resol is one or more in dimethylbenzene modified phenolic resins, epoxy resin modification resol, the organic silicon modified phenolic resin.
16. the preparation method as any described hydrophobic granule among the claim 10-15 is characterized in that, in step 2, also comprises the step that adds solidifying agent.
17. a waterproof and breathable structure is characterized in that, comprises a waterproof ventilative layer, this waterproof ventilative layer is to lay the hydrophobic granule layer that forms by any described hydrophobic granule in the claim 1～9.
18. waterproof and breathable structure according to claim 17 is characterized in that, this hydrophobic granule layer below is a basic unit.
19. waterproof and breathable structure according to claim 18 is characterized in that, the plantation hole layer of this basic unit in desert, seabeach, barren beach or soil, forming, and this hydrophobic granule layer top is the plantation soil layer.
20. waterproof and breathable structure according to claim 18 is characterized in that, this basic unit is water-bed stratum, and this hydrophobic granule layer top is the water body layer.
21. a method that forms waterproof and breathable structure is characterized in that this waterproof and breathable structure comprises a waterproof ventilative layer, this waterproof ventilative layer is laid by any described hydrophobic granule in the claim 1～9 and is formed.
22. the method for generation waterproof ventilative layer according to claim 21 is characterized in that, described waterproof ventilative layer is layed in basic unit top.
23. the method for generation waterproof ventilative layer according to claim 22 is characterized in that, the plantation hole layer of described basic unit in desert, seabeach, barren beach or soil, forming, and this hydrophobic granule layer top is the plantation soil layer.
24. the method for generation waterproof ventilative layer according to claim 22 is characterized in that, this basic unit is water-bed stratum, and this hydrophobic granule layer top is the water body layer.
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