CN109504039B - Corrosion-resistant flexible epoxy resin root-puncture-resistant waterproof composite material - Google Patents
Corrosion-resistant flexible epoxy resin root-puncture-resistant waterproof composite material Download PDFInfo
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- CN109504039B CN109504039B CN201811285837.XA CN201811285837A CN109504039B CN 109504039 B CN109504039 B CN 109504039B CN 201811285837 A CN201811285837 A CN 201811285837A CN 109504039 B CN109504039 B CN 109504039B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/83—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with metals; with metal-generating compounds, e.g. metal carbonyls; Reduction of metal compounds on textiles
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- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04D—ROOF COVERINGS; SKY-LIGHTS; GUTTERS; ROOF-WORKING TOOLS
- E04D5/00—Roof covering by making use of flexible material, e.g. supplied in roll form
- E04D5/10—Roof covering by making use of flexible material, e.g. supplied in roll form by making use of compounded or laminated materials, e.g. metal foils or plastic films coated with bitumen
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Abstract
The invention discloses a corrosion-resistant flexible epoxy resin root-puncture-resistant waterproof composite material, which is prepared by adopting a chemical plating method to prepare copper-plated glass fiber, taking the copper-plated glass fiber as a reinforcing material and a root-resisting agent, taking furan resin modified flexible epoxy resin as a matrix, and forming the corrosion-resistant flexible epoxy resin root-puncture-resistant waterproof composite material by a vacuum infusion or injection molding process. The root puncture resistant waterproof composite material prepared by the invention has higher mechanical strength, good root puncture resistance and waterproof effect, and excellent acid and alkali corrosion resistance, and can avoid the damage of the waterproof layer caused by the acid and alkali corrosion of the soil of the planted roof; the surface copper plating mode is adopted, so that the consumption of noble metal copper is greatly reduced, and the production cost is saved; the waterproof layer and the planting roof base layer can be integrated by adopting modes of vacuum infusion, injection molding and the like, the flexible epoxy resin can be cured and molded at normal temperature, and the waterproof layer has the advantages of energy conservation, environmental protection and greenness and has strong interface cohesiveness with a concrete roof.
Description
Technical Field
The invention belongs to the field of waterproof material preparation, and particularly relates to a corrosion-resistant flexible epoxy resin root-puncture-resistant waterproof composite material.
Background
The development of green planting roofs is one of effective ways for relieving the urban heat island effect and protecting the urban ecological environment, the green planting roof engineering is composed of planting, waterproofing, drainage, heat preservation and insulation and other comprehensive technologies, the roofing waterproofing technology is particularly important, and once leakage occurs, great economic loss can be caused. The root puncture-resistant waterproof material is a high-efficiency waterproof material which inhibits the root system from further growing to the waterproof layer and avoids destroying the waterproof layer, the plant root system in the planted roof system has extremely strong penetrability, and if the root puncture-resistant waterproof material is selected improperly, the root puncture-resistant waterproof material can be penetrated by plant roots to cause leakage of buildings.
The asphalt root-resistant waterproof coiled material is one of the waterproof materials with larger use amount at present, and the problems existing at present are as follows: firstly, the asphalt root-resistant waterproof roll is limited by certain length and width, so that overlapping is inevitable during use, and plant roots easily penetrate through gaps at the overlapping part, so that the gaps at the overlapping part become weak links of a waterproof system; secondly, the asphalt root-resistant waterproof coiled material is often welded by a hot-melt method in construction, so that the defects of complex process, energy consumption and high pollution are overcome, the coiled material is carbonized due to excessive hot-melt welding, the strength and the cohesiveness are reduced, the chemical root-resistant agent added in the coiled material is easily decomposed at high temperature when the chemical root-resistant agent is used, the integral root-resistant performance is poor or invalid, and the joint is formed into a virtual welding due to too short time; thirdly, the copper base of the asphalt root-resistant waterproof roll is mainly copper foil, the mechanical property and the ductility of the asphalt root-resistant waterproof roll are poor, a tire body is easy to bulge and break when meeting a corner during construction, and the internal corner part is difficult to treat; in addition, copper belongs to noble metals and is high in price, and the copper foil is used as a base, so that the using amount of copper metal is increased, and the cost is increased. The epoxy resin has excellent cohesiveness, chemical stability and mould resistance, low curing shrinkage and simple and convenient molding, so that the epoxy resin is used for waterproof coating, but the coating has the defect of poor mechanical property, and the acidity and alkalinity of soil planted on a roof easily cause the corrosion phenomenon of a coating, so that the failure of a waterproof layer is caused.
CN108250962A discloses a root resistance waterproofing membrane of non-solidification and production technology thereof sets gradually surface course, non-solidification water proof coating layer, bottom, and the surface course is the polymer film, and the bottom is the barrier film, and non-solidification water proof coating layer includes: modified petroleum asphalt, hot melt adhesive, rosin resin, adhesion promoter, polyisobutylene, root-resisting agent, talcum powder and softener. The production process comprises the following steps: mixing the modified petroleum asphalt, the hot melt adhesive, the rosin resin and the adhesion promoter to obtain a mixed matrix; mixing the mixed matrix with other raw materials to obtain a non-cured waterproof coating; the non-curing waterproof paint is coated on the bottom layer and then covered with the polymer film. CN103524947A discloses an enhanced root-resistant waterproof roll, which comprises a flame retardant, a migration-resistant plasticizer, polyvinyl chloride resin, epoxidized soybean oil, dibasic lead phosphite, tribasic lead phosphite, E-881 modified chlorine-vinegar copolymer resin and epoxy resin.
Disclosure of Invention
The invention aims to provide the corrosion-resistant flexible epoxy resin root-puncture-resistant waterproof composite material which can be cured and molded at normal temperature, is energy-saving and environment-friendly, has strong interface adhesion with a concrete planted roof, and has good corrosion resistance, root-puncture resistance and waterproof effect.
The invention aims to realize that the corrosion-resistant flexible epoxy resin root-puncture-resistant waterproof composite material is prepared by the following specific steps:
1) placing glass fiber cloth or glass fiber bundles in deoiling liquid for deoiling for 30min at 40 ℃, and placing the treated glass fiber cloth or glass fiber bundles in 10 wt% of dilute sulfuric acid to neutralize surface alkali liquor;
the deoiling liquid is as follows: 60g/L of sodium hydroxide; a mixed solution of 30g/L of sodium carbonate and 15g/L of sodium phosphate;
2) placing the glass fiber cloth or glass fiber bundle subjected to oil removal and neutralization in the step 1) into a sensitizing solution, sensitizing for 10min at 25 ℃, and repeatedly rinsing with clear water;
the sensitizing solution is as follows: mixed solution of stannous chloride 10g/L and hydrochloric acid 40 ml/L; the percentage concentration of the hydrochloric acid is 38%;
3) placing the glass fiber sensitized in the step 2) into an activating solution, activating for 10min at the temperature of 25 ℃, and enabling Pd in the solution2+The ions are converted into metal Pd particles, and then the metal Pd particles are placed in sodium hypophosphite containing 10g/L for activation for 10min to reduce the Pd on the surface2+；
The activating solution is as follows: mixed solution of 0.5g/L palladium chloride and 20ml/L hydrochloric acid; the percentage concentration of the hydrochloric acid is 38%;
4) adjusting the pH value of the copper plating solution to 9-11 by using ammonia water, placing the glass fiber cloth or glass fiber bundle activated in the step 3) into the copper plating solution for copper plating, and drying to obtain copper-plated glass fiber cloth or glass fiber bundle;
the copper plating solution comprises: 30-50g/L of copper sulfate, 20-40g/L of sodium hypophosphite, 50-70g/L of sodium citrate, 40-60g/L of ammonium chloride and 2-6mg/L of thiourea;
the copper plating temperature is 75-90 ℃, and the copper plating time is 10-30 min;
5) uniformly stirring 100 parts by mass of E51 bisphenol A epoxy resin, 34.5-60.5 parts by mass of curing agent, 10 parts by mass of plasticizer dibutyl phthalate, 25-35 parts by mass of furan resin and 2-4 parts by mass of curing accelerator to obtain a flexible epoxy resin matrix;
the curing agent is one or more of D400 polyether amine, 650 polyamide and acrylonitrile modified hexamethylene diamine;
the curing accelerator is one of nonyl phenol or 2, 4, 6-tri (dimethylaminomethyl) phenol;
the furan resin is furfural phenol resin, furfural acetone resin or furfuryl alcohol formaldehyde resin;
6) the forming method of the corrosion-resistant flexible epoxy resin root-puncture-resistant waterproof composite material comprises the following steps:
A. laying the copper-plated glass fiber cloth, the demolding cloth, the flow guide net, the flow guide pipe, the rubber inlet pipe and the vacuum bag obtained in the step 4) on a roof in sequence, sealing the vacuum bag by using a sealant, and vacuumizing until the pressure in the vacuum bag is-0.1 MPa; connecting the flexible epoxy resin matrix prepared in the step 5) with a rubber inlet pipe in a vacuum bag, introducing the flexible epoxy resin matrix into the vacuum bag in a vacuum manner, infiltrating the copper-plated glass fiber cloth in the vacuum bag, curing and forming at room temperature after the infiltration process is finished, and removing the flow guide net, the flow guide pipe and the vacuum bag by using demolding cloth; obtaining the copper-plated glass fiber reinforced flexible epoxy resin root-resistant waterproof composite material integrated with the roof;
B. spraying the flexible epoxy resin prepared in the step 5) to the surface of a roof by using a spray gun of a spray forming machine, cutting the copper-plated glass fiber bundle obtained in the step 4) into short copper-plated glass fiber bundles by using a fiber chopping device, and spraying the short copper-plated glass fiber bundles by using another spray gun; and mixing the sprayed short copper-plated glass fiber bundles with flexible epoxy resin, compacting by using a roller to enable the flexible epoxy resin to fully infiltrate the short copper-plated glass fiber bundles, and curing at normal temperature to obtain the corrosion-resistant flexible epoxy resin root-puncture-resistant waterproof composite material integrated with the roof.
The invention has the following beneficial effects:
1. the copper-plated glass fiber is used as a reinforcing material and a root-resisting agent, compared with a copper foil tire base asphalt root-resisting waterproof coiled material, the corrosion-resistant flexible epoxy resin root-puncture-resistant waterproof composite material has higher mechanical strength, can exert the chemical root-resisting effect of copper ions, can exert the physical root-resisting effect by the higher mechanical strength, and has good root-puncture-resisting and waterproof effects by combining the corrosion-resistant flexible epoxy resin root-puncture-resistant waterproof composite material and the copper foil tire base asphalt root-resisting waterproof coiled material;
2. the flexible epoxy resin is used as a matrix, polar hydroxyl and ether bonds exist in the epoxy resin, the epoxy resin has strong interface bonding performance with a concrete roof, and the furan resin has a furan ring with strong molecular stability, so that the furan resin has excellent acid-base corrosion resistance, can avoid the damage of a waterproof layer caused by acid-base corrosion of soil of a planted roof, and can improve the waterproof safety coefficient;
3. adopt forming mode such as vacuum infusion, injection molding, can realize the integration of waterproof layer and planting roofing basic unit, the production of waterproof weak links such as lap joint when avoiding the coiled material to lay, flexible epoxy can solidify the shaping at normal atmospheric temperature, can avoid the energy consumption that pitch root resistance waterproofing membrane hot melt welding caused and pollute big shortcoming, have energy-conservation, environmental protection and green advantage.
Detailed Description
The invention puts the glass fiber into degreasing liquid to degrease, neutralize; sensitizing in sensitizing solution, and repeatedly rinsing with clear water; activating in an activating solution; adjusting the pH value of the copper plating solution by ammonia water, and placing the copper plating solution in copper plating solution for copper plating; preparing a flexible epoxy resin matrix; the copper-plated glass fiber is used as a reinforcing material and a root-resisting agent, and the flexible epoxy resin is used as a matrix to form the root-puncture-resistant waterproof composite material through processes of vacuum infusion, injection molding and the like.
Adding phenyl glycidyl ether and furan resin serving as reactive diluents into the flexible epoxy resin matrix in the step 5); the flexible epoxy resin matrix is prepared by uniformly stirring 100 parts of bisphenol A type E51 epoxy resin, 34.5-60.5 parts of curing agent, 10 parts of plasticizer dibutyl phthalate, 10 parts of reactive diluent phenyl glycidyl ether, 25-35 parts of furan resin and 2-4 parts of curing accelerator in parts by mass.
The present invention is described in detail below with reference to specific examples.
Example 1
1) Arranging the glass fiber in deoiling liquid for deoiling for 30min at 40 ℃, and arranging the treated glass fiber in 10 wt% of dilute sulfuric acid to neutralize surface alkali liquor;
the formula of the deoiling liquid is as follows: 60g/L of sodium hydroxide, 30g/L of sodium carbonate and 15g/L of sodium phosphate;
2) sensitizing the glass fiber subjected to oil removal and neutralization in the step 1) in a sensitizing solution for 10min at 25 ℃, and repeatedly rinsing with clear water;
the sensitizing solution is as follows: mixed solution of stannous chloride 10g/L and hydrochloric acid 40 ml/L; the percentage concentration of hydrochloric acid was 38%.
3) Arranging the glass fiber sensitized in the step 2) in an activating solution, activating for 10min at 25 ℃, and enabling Pd in the solution2+The ions are converted into metal Pd particles, and then the metal Pd particles are placed in sodium hypophosphite containing 10g/L for 10min to reduce the Pd on the surface2+；
The activating solution is as follows: mixed solution of 0.5g/L palladium chloride and 20ml/L hydrochloric acid; the percentage concentration of hydrochloric acid was 38%.
4) Adjusting the pH value of the plating solution to 9 by using ammonia water, arranging the glass fiber activated in the step 3) in a copper plating solution, plating copper for 10min at 75 ℃, and drying to obtain copper-plated glass fiber cloth;
the copper plating solution comprises: 30g/L of copper sulfate, 20g/L of sodium hypophosphite, 50g/L of sodium citrate, 40g/L of ammonium chloride and 2mg/L of thiourea;
5) taking 100 parts by mass of bisphenol A type E51 epoxy resin, 55 parts by mass of curing agent D400 polyetheramine, 10 parts by mass of plasticizer dibutyl phthalate, 4 parts by mass of curing accelerator nonylphenol and 25 parts by mass of furfural phenol resin, and uniformly stirring by a machine to obtain a flexible epoxy resin matrix;
6) forming the corrosion-resistant flexible epoxy resin root-puncture-resistant waterproof composite material:
laying the copper-plated glass fiber cloth, the demolding cloth, the flow guide net, the flow guide pipe, the rubber inlet pipe and the vacuum bag obtained in the step 4) on a roof in sequence, sealing the vacuum bag by using a sealant, and vacuumizing until the pressure in the vacuum bag is-0.1 MPa; connecting the flexible epoxy resin matrix prepared in the step 5) with a rubber inlet pipe in a vacuum bag, introducing the flexible epoxy resin into the vacuum bag in a vacuum manner, infiltrating the copper-plated glass fiber cloth in the vacuum bag, curing and forming at normal temperature after the infiltration process is finished, and removing the flow guide net, the flow guide pipe and the vacuum bag by using demolding cloth; the corrosion-resistant flexible epoxy resin root-puncture-resistant waterproof composite material integrated with the roof is obtained.
Example 2, the same as example 1, except that,
1) the glass fiber bundle is placed in deoiling liquid to be deoiled for 30min at the temperature of 40 ℃, and the treated glass fiber bundle is placed in 10 wt% of dilute sulfuric acid to neutralize surface alkali liquor;
4) adjusting the pH value of the plating solution to 10 by using ammonia water, placing the glass fiber bundle activated in the step 3) into a copper plating solution, plating copper for 20min at 80 ℃, and drying to obtain a copper-plated glass fiber bundle;
the copper plating solution comprises: 40g/L of copper sulfate, 30g/L of sodium hypophosphite, 60g/L of sodium citrate, 50g/L of ammonium chloride and 5mg/L of thiourea;
5) taking 100 parts by mass of bisphenol A type E51 epoxy resin, 55 parts by mass of curing agent D400 polyetheramine, 10 parts by mass of plasticizer dibutyl phthalate, 4 parts by mass of curing accelerator nonylphenol and 30 parts by mass of furfural phenol resin, and uniformly stirring by a machine to obtain a flexible epoxy resin matrix;
6) forming the corrosion-resistant flexible epoxy resin root-puncture-resistant waterproof composite material:
the method comprises the following steps of firstly preparing a copper-plated glass fiber felt from a copper-plated glass fiber bundle by a wet papermaking method, wherein the specific steps of the copper-plated glass fiber felt prepared by the copper-plated glass fiber bundle wet papermaking method are as follows:
the preparation method comprises the following specific steps:
cutting the copper-plated glass fiber bundle obtained in the step 4) into a short copper-plated glass fiber bundle of 6cm,
secondly, putting the copper-plated glass fiber bundles cut in the first step into aqueous dispersion containing adhesive polyvinyl alcohol, and defibering and dispersing in a fiber dissociator at the dispersion speed of 3000rpm for 1 min;
the addition amount of the polyvinyl alcohol is 6% of the mass of the copper-plated glass fiber bundle;
the solid-liquid ratio of the aqueous dispersion of polyvinyl alcohol is 1: 10;
pouring the short copper-plated glass fiber bundle suspension obtained in the step two onto a copper mesh of a paper machine for papermaking, draining water from the dispersion through the copper mesh, and performing suction filtration for 1min to obtain a copper-plated glass fiber felt;
and fourthly, taking out the copper-plated glass fiber mat obtained in the third step, placing the copper-plated glass fiber mat in a vacuum drying device carried by a former, and drying the copper-plated glass fiber mat for 15min at the temperature of 100 ℃ to obtain the copper-plated glass fiber mat, wherein the vacuum degree is-0.1 MPa.
And then laying the obtained copper-plated glass fiber mat, the demolding cloth, the flow guide net, the flow guide pipe, the rubber inlet pipe and the vacuum bag on the roof in sequence, sealing the vacuum bag by using a sealant, and then performing the same operation as the step 1.
Example 3, the same as example 1, except that,
1) the glass fiber bundle is placed in deoiling liquid to be deoiled for 30min at the temperature of 40 ℃, and the treated glass fiber bundle is placed in 10 wt% of dilute sulfuric acid to neutralize surface alkali liquor;
4) adjusting the pH value of the plating solution to 11 by using ammonia water, placing the glass fiber bundle activated in the step 3) into a copper plating solution, and plating copper for 30min at 90 ℃ to obtain a copper-plated glass fiber bundle;
the copper plating solution comprises: 50g/L of copper sulfate, 40g/L of sodium hypophosphite, 70g/L of sodium citrate, 60g/L of ammonium chloride and 6mg/L of thiourea;
5) taking 100 parts by mass of bisphenol A type E51 epoxy resin, 55 parts by mass of curing agent D400 polyetheramine, 10 parts by mass of plasticizer dibutyl phthalate, 4 parts by mass of curing accelerator nonylphenol and 35 parts by mass of furfural phenol resin, and uniformly stirring by a machine to obtain a flexible epoxy resin matrix;
6) forming the corrosion-resistant flexible epoxy resin root-puncture-resistant waterproof composite material:
spraying the flexible epoxy resin prepared in the step 5) to the surface of a roof by using a spray gun of a spray forming machine, cutting the copper-plated glass fiber bundle obtained in the step 4) into short copper-plated glass fiber bundles by using a fiber chopping device, and spraying the short copper-plated glass fiber bundles by using another spray gun; and mixing the sprayed short copper-plated glass fiber bundles with flexible epoxy resin, compacting by using a roller to enable the flexible epoxy resin to fully infiltrate the short copper-plated glass fiber bundles, and curing at normal temperature to obtain the corrosion-resistant flexible epoxy resin root-puncture-resistant waterproof composite material integrated with the roof.
Example 4, the same as example 1, except that,
1) placing the glass fiber bundle in deoiling liquid for 30min at 40 ℃ to remove oil, and placing the treated glass fiber bundle in 10 wt% of dilute sulfuric acid to neutralize surface alkali liquor;
4) adjusting the pH value of the plating solution to 10 by using ammonia water, placing the glass fiber bundle activated in the step 3) into a copper plating solution, plating copper for 25min at 85 ℃, and drying to obtain a copper-plated glass fiber bundle;
the copper plating solution comprises: 35g/L of copper sulfate, 25g/L of sodium hypophosphite, 65g/L of sodium citrate, 58g/L of ammonium chloride and 3mg/L of thiourea;
5) uniformly mechanically stirring 100 parts of bisphenol A type E51 epoxy resin, 50 parts of curing agent 650 polyamide, 10 parts of plasticizer dibutyl phthalate, 3 parts of curing accelerator 2, 4, 6-tri (dimethylaminomethyl) phenol and 30 parts of furfural acetone resin by mass to prepare a flexible epoxy resin matrix;
6) forming the corrosion-resistant flexible epoxy resin root-puncture-resistant waterproof composite material:
spraying the flexible epoxy resin prepared in the step 5) to the surface of a roof by using a spray gun of a spray forming machine, cutting the copper-plated glass fiber bundle obtained in the step 4) into short copper-plated glass fiber bundles by using a fiber chopping device, and spraying the short copper-plated glass fiber bundles by using another spray gun; and mixing the sprayed short copper-plated glass fiber bundles with flexible epoxy resin, compacting by using a roller to enable the flexible epoxy resin to fully infiltrate the short copper-plated glass fiber bundles, and curing at normal temperature to obtain the corrosion-resistant flexible epoxy resin root-puncture-resistant waterproof composite material integrated with the roof.
Example 5, the same as example 1, except that,
1) placing the glass fiber bundle in deoiling liquid to deoil for 30min at 40 ℃, and placing the treated glass fiber in 10 wt% of dilute sulfuric acid to neutralize surface alkali liquor;
4) adjusting the pH value of the plating solution to 10 by using ammonia water, placing the glass fiber bundle activated in the step 3) into a copper plating solution, plating copper for 25min at 85 ℃, and drying to obtain a copper-plated glass fiber bundle;
the copper plating solution comprises: 45g/L of copper sulfate, 35g/L of sodium hypophosphite, 55g/L of sodium citrate, 55g/L of ammonium chloride and 5mg/L of thiourea;
5) 100 parts of bisphenol A type E51 epoxy resin, 22.5 parts of curing agent D400 polyetheramine, 12 parts of acrylonitrile modified hexamethylene diamine, 10 parts of plasticizer dibutyl phthalate, 2 parts of curing accelerator 2, 4, 6-tris (dimethylaminomethyl) phenol and 35 parts of furfural acetone resin are mechanically and uniformly stirred to prepare the flexible epoxy resin matrix.
The curing agent acrylonitrile modified hexamethylene diamine comprises the following steps:
adding 116 parts by mass of hexamethylenediamine and 100 parts by mass of diethyl ether into a three-neck flask, heating to 40 ℃ through water bath, mechanically stirring to fully dissolve the hexamethylenediamine in the diethyl ether, then adding 53 parts by mass of acrylonitrile into a diethyl ether solution of the hexamethylenediamine at a dropping speed of 10 parts/min, raising the temperature to 60 ℃, continuously stirring for reaction for 2 hours, and finally removing the diethyl ether through reduced pressure distillation to obtain the acrylonitrile-modified hexamethylenediamine. The reduced pressure distillation condition is that the temperature is 80 ℃ and the pressure is-0.1 MPa for 2 h.
6) Forming the corrosion-resistant flexible epoxy resin root-puncture-resistant waterproof composite material:
spraying the flexible epoxy resin prepared in the step 5) to the surface of a roof by using a spray gun of a spray forming machine, cutting the copper-plated glass fiber bundle obtained in the step 4) into short copper-plated glass fiber bundles by using a fiber chopping device, and spraying the short copper-plated glass fiber bundles by using another spray gun; and mixing the sprayed short copper-plated glass fiber bundles with flexible epoxy resin, compacting by using a roller to enable the flexible epoxy resin to fully infiltrate the short copper-plated glass fiber bundles, and curing at normal temperature to obtain the corrosion-resistant flexible epoxy resin root-puncture-resistant waterproof composite material integrated with the roof.
Example 6, the same as example 1, except that,
1) placing the glass fiber bundle in deoiling liquid for 30min at 40 ℃ to remove oil, and placing the treated glass fiber bundle in 10 wt% of dilute sulfuric acid to neutralize surface alkali liquor;
4) adjusting the pH value of the plating solution to 11 by using ammonia water, placing the glass fiber bundle activated in the step 3) into a copper plating solution, plating copper for 25min at 85 ℃, and drying to obtain a copper-plated glass fiber bundle;
the copper plating solution comprises: 42g/L of copper sulfate, 28g/L of sodium hypophosphite, 62g/L of sodium citrate, 48g/L of ammonium chloride and 4mg/L of thiourea;
5) taking 100 parts by mass of bisphenol A type E51 epoxy resin, 10 parts by mass of phenyl glycidyl ether serving as an active diluent, 60.5 parts by mass of curing agent D400 polyether amine, 10 parts by mass of dibutyl phthalate serving as a plasticizer, 4 parts by mass of nonyl phenol serving as a curing accelerator and 30 parts by mass of furfuryl alcohol formaldehyde resin, and uniformly stirring by a machine to obtain a flexible epoxy resin matrix;
6) forming the corrosion-resistant flexible epoxy resin root-puncture-resistant waterproof composite material:
spraying the flexible epoxy resin prepared in the step 5) to the surface of a roof by using a spray gun of a spray forming machine, cutting the copper-plated glass fiber bundle obtained in the step 4) into short copper-plated glass fiber bundles by using a fiber chopping device, and spraying the short copper-plated glass fiber bundles by using another spray gun; and mixing the sprayed short copper-plated glass fiber bundles with flexible epoxy resin, compacting by using a roller to enable the flexible epoxy resin to fully infiltrate the short copper-plated glass fiber bundles, and curing at normal temperature to obtain the corrosion-resistant flexible epoxy resin root-puncture-resistant waterproof composite material integrated with the roof.
The applicant performs performance tests on the corrosion-resistant flexible epoxy resin root penetration resistant waterproof composite material obtained in each embodiment according to national standards GB 1447-2005, GB/T328.10-2007 and industrial standards JC/T1075-2008, and the test results of the embodiments 1-6 are shown in the following table.
As can be seen from the table, the invention has good tensile strength, impermeability, root penetration resistance and acid-base corrosion resistance.
Claims (5)
1. The utility model provides a waterproof combined material of root resistance puncture of corrosion-resistant flexible epoxy which characterized in that: the preparation method comprises the following specific steps:
1) placing glass fiber cloth or glass fiber bundles in deoiling liquid for deoiling for 30min at 40 ℃, and placing the treated glass fiber cloth or glass fiber bundles in 10 wt% of dilute sulfuric acid to neutralize surface alkali liquor;
the deoiling liquid is as follows: 60g/L of sodium hydroxide; a mixed solution of 30g/L of sodium carbonate and 15g/L of sodium phosphate;
2) placing the glass fiber cloth or glass fiber bundle subjected to oil removal and neutralization in the step 1) into a sensitizing solution, sensitizing for 10min at 25 ℃, and repeatedly rinsing with clear water;
the sensitizing solution is as follows: mixed solution of stannous chloride 10g/L and hydrochloric acid 40 ml/L; the percentage concentration of the hydrochloric acid is 38%;
3) placing the glass fiber sensitized in the step 2) into an activating solution, activating for 10min at the temperature of 25 ℃, and enabling Pd in the solution2 +The ions are converted into metal Pd particles, and then the metal Pd particles are placed in sodium hypophosphite containing 10g/L for activation for 10min to reduce the Pd on the surface2+；
The activating solution is as follows: mixed solution of 0.5g/L palladium chloride and 20ml/L hydrochloric acid; the percentage concentration of the hydrochloric acid is 38%;
4) adjusting the pH value of the copper plating solution to 9-11 by using ammonia water, placing the glass fiber cloth or glass fiber bundle activated in the step 3) into the copper plating solution for copper plating, and drying to obtain copper-plated glass fiber cloth or glass fiber bundle;
the copper plating solution comprises: 30-50g/L of copper sulfate, 20-40g/L of sodium hypophosphite, 50-70g/L of sodium citrate, 40-60g/L of ammonium chloride and 2-6mg/L of thiourea;
the copper plating temperature is 75-90 ℃, and the copper plating time is 10-30 min;
5) uniformly stirring 100 parts by mass of E51 bisphenol A epoxy resin, 34.5-60.5 parts by mass of curing agent, 10 parts by mass of plasticizer dibutyl phthalate, 25-35 parts by mass of furan resin and 2-4 parts by mass of curing accelerator to obtain a flexible epoxy resin matrix;
the curing agent is one or more of D400 polyether amine, 650 polyamide and acrylonitrile modified hexamethylene diamine;
the curing accelerator is one of nonyl phenol or 2, 4, 6-tri (dimethylaminomethyl) phenol;
the furan resin is furfural phenol resin, furfural acetone resin or furfuryl alcohol formaldehyde resin;
6) the forming method of the corrosion-resistant flexible epoxy resin root-puncture-resistant waterproof composite material comprises the following steps:
A. laying the copper-plated glass fiber cloth, the demolding cloth, the flow guide net, the flow guide pipe, the rubber inlet pipe and the vacuum bag obtained in the step 4) on a roof in sequence, sealing the vacuum bag by using a sealant, and vacuumizing until the pressure in the vacuum bag is-0.1 MPa; connecting the flexible epoxy resin matrix prepared in the step 5) with a rubber inlet pipe in a vacuum bag, introducing the flexible epoxy resin matrix into the vacuum bag in a vacuum manner, infiltrating the copper-plated glass fiber cloth in the vacuum bag, curing and forming at room temperature after the infiltration process is finished, and removing the flow guide net, the flow guide pipe and the vacuum bag by using demolding cloth; obtaining the copper-plated glass fiber reinforced flexible epoxy resin root-resistant waterproof composite material integrated with the roof;
B. spraying the flexible epoxy resin prepared in the step 5) to the surface of a roof by using a spray gun of a spray forming machine, cutting the copper-plated glass fiber bundle obtained in the step 4) into short copper-plated glass fiber bundles by using a fiber chopping device, and spraying the short copper-plated glass fiber bundles by using another spray gun; and mixing the sprayed short copper-plated glass fiber bundles with flexible epoxy resin, compacting by using a roller to enable the flexible epoxy resin to fully infiltrate the short copper-plated glass fiber bundles, and curing at normal temperature to obtain the corrosion-resistant flexible epoxy resin root-puncture-resistant waterproof composite material integrated with the roof.
2. The corrosion-resistant flexible epoxy root-puncture-resistant waterproof composite material according to claim 1, characterized in that: and 4) preparing the copper-plated glass fiber felt from the copper-plated glass fiber bundle obtained in the step 4) by a wet papermaking method.
3. The corrosion-resistant flexible epoxy root-penetration-resistant waterproof composite material of claim 2, wherein: the method for preparing the copper-plated glass fiber felt by the copper-plated glass fiber bundle wet papermaking method comprises the following specific steps:
cutting the copper-plated glass fiber bundle obtained in the step 4) into a short copper-plated glass fiber bundle of 6 cm;
secondly, putting the copper-plated glass fiber bundles cut in the first step into aqueous dispersion containing adhesive polyvinyl alcohol, and defibering and dispersing in a fiber dissociator at the dispersion speed of 3000rpm for 1 min;
the addition amount of the polyvinyl alcohol is 6% of the mass of the copper-plated glass fiber bundle;
the solid-liquid ratio of the aqueous dispersion of polyvinyl alcohol is 1: 10;
pouring the short copper-plated glass fiber bundle suspension obtained in the step two onto a copper mesh of a paper machine for papermaking, draining water from the dispersion through the copper mesh, and performing suction filtration for 1min to obtain a copper-plated glass fiber felt;
and fourthly, taking out the copper-plated glass fiber mat obtained in the third step, placing the copper-plated glass fiber mat in a vacuum drying device carried by a former, and drying the copper-plated glass fiber mat for 15min at the temperature of 100 ℃ to obtain the copper-plated glass fiber mat, wherein the vacuum degree is-0.1 Mpa.
4. The corrosion-resistant flexible epoxy root-puncture-resistant waterproof composite material according to claim 1, characterized in that: adding phenyl glycidyl ether and furan resin serving as reactive diluents into the flexible epoxy resin matrix in the step 5); the flexible epoxy resin matrix is prepared by uniformly stirring 100 parts of bisphenol A type E51 epoxy resin, 34.5-60.5 parts of curing agent, 10 parts of plasticizer dibutyl phthalate, 10 parts of reactive diluent phenyl glycidyl ether, 25-35 parts of furan resin and 2-4 parts of curing accelerator in parts by mass.
5. The corrosion-resistant flexible epoxy root-puncture-resistant waterproof composite material according to claim 1, characterized in that: the curing agent acrylonitrile modified hexamethylene diamine in the step 5) comprises the following steps:
adding 116 parts by mass of hexamethylenediamine and 100 parts by mass of diethyl ether into a three-neck flask, heating to 40 ℃ through water bath, mechanically stirring to fully dissolve the hexamethylenediamine in the diethyl ether, then adding 53 parts by mass of acrylonitrile into a diethyl ether solution of the hexamethylenediamine at a dropping speed of 10 parts/min, raising the temperature to 60 ℃, continuously stirring for reaction for 2 hours, and finally removing the diethyl ether through reduced pressure distillation to obtain acrylonitrile-modified hexamethylenediamine; the reduced pressure distillation condition is that the temperature is 80 ℃ and the pressure is-0.1 MPa for 2 h.
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