WO2023006123A1 - Normal-temperature in-situ repair material for drainage pipeline, and construction method therefor - Google Patents

Normal-temperature in-situ repair material for drainage pipeline, and construction method therefor Download PDF

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Publication number
WO2023006123A1
WO2023006123A1 PCT/CN2022/111363 CN2022111363W WO2023006123A1 WO 2023006123 A1 WO2023006123 A1 WO 2023006123A1 CN 2022111363 W CN2022111363 W CN 2022111363W WO 2023006123 A1 WO2023006123 A1 WO 2023006123A1
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Prior art keywords
parts
add
stir
situ repair
drainage pipes
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PCT/CN2022/111363
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French (fr)
Chinese (zh)
Inventor
李通
李佳川
李万朝
张�杰
俞发兰
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上海誉帆环境科技股份有限公司
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Publication of WO2023006123A1 publication Critical patent/WO2023006123A1/en

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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
    • C08L63/10—Epoxy resins modified by unsaturated compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
    • C08F283/105—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule on to unsaturated polymers containing more than one epoxy radical per molecule
    • E—FIXED CONSTRUCTIONS
    • E03—WATER SUPPLY; SEWERAGE
    • E03F—SEWERS; CESSPOOLS
    • E03F3/00—Sewer pipe-line systems
    • E03F3/06—Methods of, or installations for, laying sewer pipes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/18—Applications used for pipes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/18—Spheres
    • 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
    • Y02A20/00—Water conservation; Efficient water supply; Efficient water use
    • Y02A20/20—Controlling water pollution; Waste water treatment

Definitions

  • the invention relates to the technical field of pipeline repair, in particular to a normal-temperature in-situ repair material for drainage pipelines and a construction method thereof.
  • the in-situ curing repair process is one of the most widely used processes in the repair of drainage pipes.
  • the most widely used construction processes in China include the overturning heat curing method and the pull-in ultraviolet light curing method.
  • the overturning heat curing repair construction requires sufficient overturning construction space on site, at least one inspection well for the pipe section to be repaired, and the site and space required for placing overturning equipment, hot water heating system, etc. Enough water to ensure that the flipping construction goes smoothly.
  • the UV curing repair construction requires that the inspection wells at both ends of the pipe section have operating space.
  • the lining hose is placed at the position of the inspection well at one end, and the hoist is fixed at the other end of the inspection well to pull the material.
  • the site requirements for the construction site are relatively strict. During the curing process There also needs to be enough space and site for curing equipment.
  • Patent application CN110746552A discloses an in-situ curing repair resin, which is composed of A material and B material, A material includes curable resin, reactive diluent, crosslinking agent and filler, etc., B material is a curing agent, and the curable Resins include acrylic resins, polycarbonate resins, polylactic acid resins, polyethylene glycol, and the like.
  • the mechanical properties of the cured resin in this patent application are not good, and the corrosion resistance mainly depends on the addition of nano-silver powder, which is costly and has an unsatisfactory repair effect on drainage pipes.
  • the object of the present invention is to provide a normal temperature in-situ repair material for drainage pipes and its construction method, which can improve mechanical properties and corrosion resistance, and have good repairability for drainage pipes.
  • a normal-temperature in-situ repair material for drainage pipes which includes two parts, material A and material B.
  • material A is composed of 100 parts of novolac epoxy acrylate, 80-100 parts of bisphenol A epoxy diacrylate Obtained by uniform mixing of acrylate and 30-40 parts of 2-ethyl methacrylate;
  • the preparation method of material B is as follows:
  • the specific method of step (1) is: first mix 50-60 parts of glycidyl methacrylate, 35-45 parts of ethylene glycol dimethacrylate, 35-45 parts of phthalate Stir and mix diethyl formate and 2-3 parts of benzoyl peroxide to obtain the oil phase; then add 8-10 parts of polyvinyl alcohol to 1000 parts of water, stir and mix to obtain the water phase; then mix the oil phase while stirring Slowly and uniformly drop the phase into the water phase. After the dropwise addition, stir and react at 80-85°C and 500-600r/min for 3-4 hours, cool to room temperature naturally, centrifuge, and wash with water to obtain the porous microstructure. ball.
  • the time for adding the oil phase is 30 to 40 minutes, and the particle size of the porous microspheres is 5 ⁇ m or less.
  • step (2) is as follows: first mix 1 part of porous microspheres,
  • reaction time is 6-8 hours.
  • the specific method of step (3) is as follows: first add 1 part of tetrakis(p-carboxyphenyl)porphyrin to 4-5 parts of N,N'-dimethylformamide, stir and disperse evenly , followed by adding 1-2 parts of pyridine, stirring and mixing, and then adding 0.02-0.03 parts of titanium tetrachloride while stirring under the protection of nitrogen, stirring and reacting, and post-processing to obtain the titanium porphyrin complex.
  • the process condition of the stirring reaction is: stirring and reacting at 140-150°C for 5-6 hours.
  • the specific post-treatment method is as follows: use a chloroform-methanol mixture with a volume ratio of 6:1 for silica gel column chromatography separation, rotary evaporation to remove the solvent, and then dry.
  • the above-mentioned construction method for normal temperature in-situ repair materials for drainage pipes firstly mixes material A and material B to obtain a resin mother liquor, then fully impregnates the hose with the resin mother liquor, and rolls it to the designed thickness. Then use the gas turning equipment to turn over the hose, and use the air compressor to push the hose to the position to be repaired, and continue to inflate the hose to make the hose and the pipeline to be repaired closely, maintain the air pressure, and the curing reaction occurs. After the curing is completed, the device can be removed.
  • the immersion time is 10-15 minutes
  • the air pressure is maintained at 0.5-0.8 MPa
  • the curing reaction time is 20-30 minutes.
  • the invention provides a normal temperature in-situ repair material for drainage pipes, which includes two parts, material A and material B.
  • Material A is a combination of novolac epoxy acrylate, bisphenol A epoxy diacrylate and 2-methyl Ethyl acrylate is uniformly mixed.
  • Material B is 4-vinylbenzaldehyde, photoinitiator 1173, azobisisobutyronitrile, coumarin-porous microsphere complex, titanium porphyrin complex, dichloromethane , Trifluoroacetic acid obtained by uniform mixing.
  • material A and material B ready to use, easy to use, has high mechanical properties and corrosion resistance, and has good repairability for drainage pipes.
  • the advantages of the present invention are as follows:
  • the construction site only needs an air compressor and a gas turning platform to complete the entire repair construction, without additional water supply and material pulling equipment, especially suitable for pipeline repair construction that is difficult to reach directly on the construction site.
  • the curing process does not require boilers and light curing vehicles. It is only necessary to maintain sufficient air pressure in the hose during the curing process, and only an air compressor is needed to maintain the pressure during the curing process.
  • the hose is impregnated and pressed on site, so there is no need to worry about the lining hose being solidified during transportation, and the construction time can be arranged in a reasonable and timely manner according to the dredging situation on site. Fully coordinate the overall construction time.
  • the construction process has high requirements for engineering personnel. It is necessary to reasonably arrange the overall construction process according to the curing time of the resin, and install it in place before the resin is cured. For projects with more urgent requirements, the overall construction process can be intuitive. exhibit.
  • titanium porphyrin complex acts as a catalyst to promote resin polymerization. Because of its special spatial structure, it can promote more abundant branching of epoxy structure polymerization, and the formation of branched structure helps to improve mechanical properties and corrosion resistance. Properties; the coumarin-porous microsphere composite acts as a filler and is uniformly dispersed in the system to further improve mechanical properties and corrosion resistance.
  • the preparation of coumarin-porous microsphere composite is to prepare porous microspheres with glycidyl methacrylate and ethylene glycol dimethacrylate as raw materials, and then prepare porous microspheres, 3-aminophenol, acetyl Ethyl acetate is added to absolute ethanol, and zinc chloride is used as a catalyst to stir and react.
  • the generated coumarin is deposited on the surface or pores of porous microspheres, and the particle size of the composite is controlled to ensure that it is in the It is uniformly dispersed in the system, and at the same time, it plays a buffer role with the help of porous microspheres to improve mechanical properties and corrosion resistance.
  • a normal temperature in-situ repair material for drainage pipes which includes two parts, A material and B material, A material is 100kg novolac epoxy acrylate, 80kg bisphenol A epoxy diacrylate, 40kg Obtained by uniform mixing of 2- ethyl methacrylate;
  • the preparation method of material B is as follows:
  • step (1) The specific method of step (1) is: first stir and mix 60kg glycidyl methacrylate, 35kg ethylene glycol dimethacrylate, 45kg diethyl phthalate and 2kg benzoyl peroxide to obtain oil Phase; then 10kg Add polyvinyl alcohol into 1000kg of water, stir and mix to obtain the water phase; then slowly and uniformly drop the oil phase into the water phase while stirring, after the dropwise addition, stir and react at 80°C and 600r/min for 3 hours, naturally Cool to room temperature, centrifuge and wash with water to obtain the porous microspheres.
  • the dropping time of the oil phase was 40 minutes, and the particle size of the porous microspheres was below 5 ⁇ m.
  • step (2) The specific method of step (2) is as follows: first mix 1kg of porous microspheres, 0.3kg of 3-aminophenol, 0.3kg Add ethyl acetoacetate to 5kg absolute ethanol, stir and mix well, then add 0.5kg of zinc chloride, under the protection of nitrogen, heated to reflux, heat preservation and stirring reaction, naturally cooled to room temperature after the reaction, added 4kg of 38% hydrochloric acid in mass concentration, stirred and mixed, filtered, washed with water, dried to obtain the Coumarin-porous microsphere complex.
  • the reaction time is 6 hours.
  • step (3) The specific method of step (3) is as follows: first add 1kg of tetrakis(p-carboxyphenyl)porphyrin to 5kg of N,N'-dimethylformamide, stir and disperse evenly, then add 1kg of pyridine, stir and mix, and then Under protection, add 0.03 kg of titanium tetrachloride while stirring, react with stirring, and perform post-treatment to obtain the titanium porphyrin complex.
  • the process condition of stirring reaction is: 140°C stirring reaction for 6 hours.
  • the specific post-treatment method is as follows: use a chloroform-methanol mixture with a volume ratio of 6:1 for silica gel column chromatography, rotary evaporation to remove the solvent, and then dry.
  • a normal temperature in-situ repair material for drainage pipes which includes two parts, A material and B material, A material is 100kg novolac epoxy acrylate, 100kg bisphenol A epoxy diacrylate, 30kg Obtained by uniform mixing of 2- ethyl methacrylate;
  • the preparation method of material B is as follows:
  • step (1) The specific method of step (1) is: first stir and mix 50kg glycidyl methacrylate, 45kg ethylene glycol dimethacrylate, 35kg diethyl phthalate and 3kg benzoyl peroxide to obtain oil Then add 8kg of polyvinyl alcohol into 1000kg of water, stir and mix to obtain the water phase; then add the oil phase to the water phase slowly and uniformly while stirring, after the addition is completed, stir at 85°C and 500r/min React for 4 hours, naturally cool to room temperature, centrifuge and wash with water to obtain the porous microspheres.
  • the dropping time of the oil phase was 30 minutes, and the particle size of the porous microspheres was below 5 ⁇ m.
  • step (2) The specific method of step (2) is as follows: first mix 1kg of porous microspheres, 0.5kg of 3-aminophenol, 0.2kg Add ethyl acetoacetate to 7kg of absolute ethanol, stir and mix well, then add 0.3kg of zinc chloride, under the protection of nitrogen, heated to reflux, heat preservation and stirring reaction, naturally cooled to room temperature after the reaction, added 5kg of 36% hydrochloric acid in mass concentration, stirred and mixed, filtered, washed with water, dried to obtain the Coumarin-porous microsphere complex.
  • the reaction time is 8 hours.
  • step (3) The specific method of step (3) is as follows: first add 1kg of tetrakis(p-carboxyphenyl)porphyrin to 4kg of N,N'-dimethylformamide, stir and disperse evenly, then add 2kg of pyridine, stir and mix, and then Under protection, add 0.02 kg of titanium tetrachloride while stirring, react with stirring, and perform post-treatment to obtain the titanium porphyrin complex.
  • the process conditions of the stirring reaction are: 150°C stirring reaction for 5 hours.
  • the specific post-treatment method is as follows: use a chloroform-methanol mixture with a volume ratio of 6:1 for silica gel column chromatography, rotary evaporation to remove the solvent, and then dry.
  • a normal temperature in-situ repair material for drainage pipes which includes two parts A material and B material, A material is 100kg novolac epoxy acrylate, 90kg bisphenol A epoxy diacrylate, 35kg Obtained by uniform mixing of 2- ethyl methacrylate;
  • the preparation method of material B is as follows:
  • step (1) The specific method of step (1) is: first stir and mix 55kg glycidyl methacrylate, 40kg ethylene glycol dimethacrylate, 40kg diethyl phthalate and 2.5kg benzoyl peroxide to obtain oil phase; then add 9kg of polyvinyl alcohol into 1000kg of water, stir and mix well to obtain the water phase; then slowly add the oil phase to the water phase while stirring, and after the addition is completed, under the conditions of 82°C and 600r/min Stir the reaction for 3.5 hours, naturally cool to room temperature, centrifuge, and wash with water to obtain the porous microspheres.
  • the dropping time of the oil phase was 35 minutes, and the particle size of the porous microspheres was below 5 ⁇ m.
  • step (2) The specific method of step (2) is as follows: first mix 1kg of porous microspheres, 0.4kg of 3-aminophenol, 0.25kg Add ethyl acetoacetate to 6kg of absolute ethanol, stir and mix well, then add 0.4kg zinc chloride, under nitrogen protection, heated to reflux, heat preservation and stirring reaction, naturally cooled to room temperature after the reaction, added 4.5kg mass concentration 37% hydrochloric acid, stirred and mixed, filtered, washed with water, dried to obtain the described coumarin-porous microsphere complexes.
  • the reaction time is 7 hours.
  • step (3) The specific method of step (3) is as follows: first add 1kg of tetrakis(p-carboxyphenyl)porphyrin to 4.5kg of N,N’-dimethylformamide, stir and disperse evenly, then add 1.5kg of pyridine, stirred and mixed, and then under the protection of nitrogen, 0.025kg of titanium tetrachloride was added while stirring, stirred and reacted, and post-treated to obtain the titanium porphyrin complex.
  • the process condition of the stirring reaction is: stirring reaction at 145°C for 5.5 hours.
  • the specific post-treatment method is as follows: use a chloroform-methanol mixture with a volume ratio of 6:1 for silica gel column chromatography, rotary evaporation to remove the solvent, and then dry.
  • a normal temperature in-situ repair material for drainage pipes which includes two parts, A material and B material, A material is 100kg novolac epoxy acrylate, 80kg bisphenol A epoxy diacrylate, 40kg Obtained by uniform mixing of 2- ethyl methacrylate;
  • the preparation method of material B is as follows:
  • step (1) The specific method of step (1) is: first stir and mix 60kg glycidyl methacrylate, 35kg ethylene glycol dimethacrylate, 45kg diethyl phthalate and 2kg benzoyl peroxide to obtain oil Phase; then 10kg Add polyvinyl alcohol into 1000kg of water, stir and mix to obtain the water phase; then slowly and uniformly drop the oil phase into the water phase while stirring, after the dropwise addition, stir and react at 80°C and 600r/min for 3 hours, naturally Cool to room temperature, centrifuge and wash with water to obtain the porous microspheres.
  • the dropping time of the oil phase was 40 minutes, and the particle size of the porous microspheres was below 5 ⁇ m.
  • step (2) The specific method of step (2) is as follows: first add 1kg tetrakis(p-carboxyphenyl)porphyrin to 5kgN,N’
  • the process condition of stirring reaction is: 140°C stirring reaction for 6 hours.
  • the specific post-treatment method is as follows: use a chloroform-methanol mixture with a volume ratio of 6:1 for silica gel column chromatography, rotary evaporation to remove the solvent, and then dry.
  • a normal temperature in-situ repair material for drainage pipes which includes two parts, A material and B material, A material is 100kg novolac epoxy acrylate, 80kg bisphenol A epoxy diacrylate, 40kg Obtained by uniform mixing of 2- ethyl methacrylate;
  • the preparation method of material B is as follows:
  • step (1) The specific method of step (1) is as follows: first add 1kg of tetrakis(p-carboxyphenyl)porphyrin to 5kg of N,N'-dimethylformamide, stir and disperse evenly, then add 1kg of pyridine, stir and mix, and then Under protection, add 0.03 kg of titanium tetrachloride while stirring, react with stirring, and perform post-treatment to obtain the titanium porphyrin complex.
  • the process condition of stirring reaction is: 140°C stirring reaction for 6 hours.
  • the specific post-treatment method is as follows: use a chloroform-methanol mixture with a volume ratio of 6:1 for silica gel column chromatography, rotary evaporation to remove the solvent, and then dry.
  • a normal temperature in-situ repair material for drainage pipes which includes two parts A material and B material, A material is 100kg novolac epoxy acrylate, 80kg bisphenol A epoxy diacrylate, 40kg Obtained by uniform mixing of 2- ethyl methacrylate;
  • the preparation method of material B is as follows:
  • step (1) The specific method of step (1) is: first stir and mix 60kg glycidyl methacrylate, 35kg ethylene glycol dimethacrylate, 45kg diethyl phthalate and 2kg benzoyl peroxide to obtain oil Phase; then 10kg Add polyvinyl alcohol into 1000kg of water, stir and mix to obtain the water phase; then slowly and uniformly drop the oil phase into the water phase while stirring, after the dropwise addition, stir and react at 80°C and 600r/min for 3 hours, the natural Cool to room temperature, centrifuge and wash with water to obtain the porous microspheres.
  • the dropping time of the oil phase was 40 minutes, and the particle size of the porous microspheres was below 5 ⁇ m.
  • step (2) The specific method of step (2) is as follows: first mix 1kg of porous microspheres, 0.3kg of 3-aminophenol, 0.3kg Add ethyl acetoacetate to 5kg absolute ethanol, stir and mix well, then add 0.5kg of zinc chloride, under the protection of nitrogen, heated to reflux, heat preservation and stirring reaction, naturally cooled to room temperature after the reaction, added 4kg of 38% hydrochloric acid in mass concentration, stirred and mixed, filtered, washed with water, dried to obtain the Coumarin-porous microsphere complex.
  • the reaction time is 6 hours.
  • the repair materials obtained in Examples 1-3 and Comparative Examples 1-3 were respectively used for the repair of drainage pipes.
  • the specific method is as follows: First, stir and mix materials A and B to obtain a resin mother liquor, and then use the resin mother liquor to clean the hose. Fully impregnate (impregnation time is 12 minutes), and roll to the design thickness, then use the air turning equipment to turn over the hose, and use the air compressor to push the hose to the position to be repaired, and continue to inflate the hose to make the soft
  • the tube fits closely with the pipeline to be repaired to maintain air pressure 0.7Ma, the curing reaction occurs (the curing reaction time is 25 minutes), and the device can be removed after the curing is completed.

Abstract

Disclosed in the present invention are a normal-temperature in-situ repair material for a drainage pipeline and a construction method therefor. The normal-temperature in-situ repair material comprises a material A and a material B. The material A is obtained by uniformly mixing phenolic epoxy acrylate, bisphenol A epoxy diacrylate and 2-ethyl methacrylate. The material B is obtained by uniformly mixing 4-vinylbenzaldehyde, photoinitiator 1173, azodiisobutyronitrile, a coumarin-porous microsphere compound, a titanium porphyrin complex, dichloromethane and trifluoroacetic acid. During construction, the material A and the material B are directly stirred and mixed uniformly, are immediately ready for use, are convenient to use, have high mechanical properties and corrosion resistance, and have good repair performance on a drainage pipeline.

Description

一种用于排水管道的常温原位修复材料及其施工方法A normal temperature in-situ repair material for drainage pipes and its construction method 技术领域technical field
本发明涉及管道修复技术领域，特别是涉及一种用于排水管道的常温原位修复材料及其施工方法。The invention relates to the technical field of pipeline repair, in particular to a normal-temperature in-situ repair material for drainage pipelines and a construction method thereof.
背景技术Background technique
原位固化修复工艺是目前排水管道修复施工中应用较为广泛的工艺之一，目前在国内应用较为广泛的施工工艺包括翻转热固化法、拉入式紫外光固化法等工艺。The in-situ curing repair process is one of the most widely used processes in the repair of drainage pipes. At present, the most widely used construction processes in China include the overturning heat curing method and the pull-in ultraviolet light curing method.
翻转热固化修复施工需要现场具有足够的翻转施工空间，待修复管段 至少需要有一端检查井，且检查井周边具有放置翻转设备、热水加热*** 等所需的场地和空间，且在加热时需要足够的水来保证翻转施工顺利进行。The overturning heat curing repair construction requires sufficient overturning construction space on site, at least one inspection well for the pipe section to be repaired, and the site and space required for placing overturning equipment, hot water heating system, etc. Enough water to ensure that the flipping construction goes smoothly.
紫外光固化修复施工则需要管段两端的检查井都具有操作空间，一端检查井位置处放置内衬软管，另一端检查井固定卷扬机牵拉材料，对施工现场的场地要求较为严格，固化过程时还需要有足够放置固化设备的空间和场地。The UV curing repair construction requires that the inspection wells at both ends of the pipe section have operating space. The lining hose is placed at the position of the inspection well at one end, and the hoist is fixed at the other end of the inspection well to pull the material. The site requirements for the construction site are relatively strict. During the curing process There also needs to be enough space and site for curing equipment.
上述两种修复工艺对于道路下方的管道开展修复施工时，无需考虑场地的限制因素。但是对于一些分布在河道或者车辆难以达到的管道时，需要搭设足够多的辅助设施方可完成修复施工。针对这些特殊的施工管道， 特别是受制于施工场地以及环境限制的管道，可以采用常温原位固化修复工艺。The above two restoration techniques do not need to consider the limiting factors of the site when repairing the pipeline under the road. However, for some pipelines distributed in rivers or difficult for vehicles to reach, it is necessary to build enough auxiliary facilities to complete the repair work. For these special construction pipelines, especially pipelines subject to construction site and environmental restrictions, the normal temperature in-situ curing repair process can be used.
专利申请 CN110746552A 公开了一种原位固化修复树脂，是由 A 料和 B 料组成，A 料包括固化性树脂、反应稀释剂、交联剂和填料等，B 料为固化剂，其中，固化性树脂包括丙烯酸树脂、聚碳酸酯树脂、聚乳酸树脂、聚乙二醇等。该专利申请的树脂固化后的机械性能欠佳，耐腐蚀性主要依赖于纳米银粉的加入，成本高，对排水管道的修复效果不理想。Patent application CN110746552A discloses an in-situ curing repair resin, which is composed of A material and B material, A material includes curable resin, reactive diluent, crosslinking agent and filler, etc., B material is a curing agent, and the curable Resins include acrylic resins, polycarbonate resins, polylactic acid resins, polyethylene glycol, and the like. The mechanical properties of the cured resin in this patent application are not good, and the corrosion resistance mainly depends on the addition of nano-silver powder, which is costly and has an unsatisfactory repair effect on drainage pipes.
技术解决方案technical solution
本发明的目的就是要提供一种用于排水管道的常温原位修复材料及其施工方法，提高机械性能和耐腐蚀性，对排水管道具有良好的修复性。The object of the present invention is to provide a normal temperature in-situ repair material for drainage pipes and its construction method, which can improve mechanical properties and corrosion resistance, and have good repairability for drainage pipes.
为实现上述目的，本发明是通过如下方案实现的：To achieve the above object, the present invention is achieved through the following scheme:
一种用于排水管道的常温原位修复材料，其包括 A 料和 B 料两部分， 以重量份计，A 料是将 100 份酚醛环氧丙烯酸酯、80～100 份双酚 A 环氧二丙烯酸酯、30～40 份 2-甲基丙烯酸乙酯均匀混合而得；A normal-temperature in-situ repair material for drainage pipes, which includes two parts, material A and material B. In parts by weight, material A is composed of 100 parts of novolac epoxy acrylate, 80-100 parts of bisphenol A epoxy diacrylate Obtained by uniform mixing of acrylate and 30-40 parts of 2-ethyl methacrylate;
B 料的制备方法如下：The preparation method of material B is as follows:
（1）先以甲基丙烯酸缩水甘油酯和二甲基丙烯酸乙二醇酯为原料制备多孔微球；(1) First prepare porous microspheres with glycidyl methacrylate and ethylene glycol dimethacrylate as raw materials;
（2）然后将多孔微球、3-氨基酚、乙酰乙酸乙酯加入无水乙醇中，以氯化锌为催化剂，搅拌反应，得到香豆素-多孔微球复合物；(2) Then add porous microspheres, 3-aminophenol, and ethyl acetoacetate into absolute ethanol, use zinc chloride as a catalyst, and stir for reaction to obtain a coumarin-porous microsphere composite;
（3）再以四（对羧基苯基）卟啉和四氯化钛为原料，氮气保护下反应得到钛卟啉配合物；(3) taking tetrakis(p-carboxyphenyl)porphyrin and titanium tetrachloride as raw materials, reacting under nitrogen protection to obtain titanium porphyrin complex;
（4）最后将 0.2～0.3 份 4-乙烯基苯甲醛、1～2 份光引发剂 1173、1～2 份偶氮二异丁腈、1～2 份香豆素-多孔微球复合物、0.3～0.5 份钛卟啉配合物、7～9 份二氯甲烷、1～2 份三氟乙酸均匀混合即得。(4) Finally, 0.2-0.3 parts of 4-vinylbenzaldehyde, 1-2 parts of photoinitiator 1173, 1-2 parts of azobisisobutyronitrile, 1-2 parts of coumarin-porous microsphere complex, 0.3-0.5 parts of titanium porphyrin complex, 7-9 parts of dichloromethane, and 1-2 parts of trifluoroacetic acid are uniformly mixed.
优选的，以重量份计，步骤（1）的具体方法为：先将 50～60 份甲基丙烯酸缩水甘油酯、35～45 份二甲基丙烯酸乙二醇酯、35～45 份邻苯二甲酸二乙酯和 2～3 份过氧化苯甲酰搅拌混匀，得到油相；然后将 8～10 份聚乙烯醇加入 1000 份水中，搅拌混匀，得到水相；接着边搅拌边将油相缓慢匀速滴加至水相中，滴加完毕后，80～85℃和 500～600r/min 条件下搅拌反应 3～4 小时，自然冷却至室温，离心，水洗，即得所述的多孔微球。Preferably, in terms of parts by weight, the specific method of step (1) is: first mix 50-60 parts of glycidyl methacrylate, 35-45 parts of ethylene glycol dimethacrylate, 35-45 parts of phthalate Stir and mix diethyl formate and 2-3 parts of benzoyl peroxide to obtain the oil phase; then add 8-10 parts of polyvinyl alcohol to 1000 parts of water, stir and mix to obtain the water phase; then mix the oil phase while stirring Slowly and uniformly drop the phase into the water phase. After the dropwise addition, stir and react at 80-85°C and 500-600r/min for 3-4 hours, cool to room temperature naturally, centrifuge, and wash with water to obtain the porous microstructure. ball.
进一步优选的，油相的滴加时间为 30～40 分钟，多孔微球的粒径为 5μm 以下。More preferably, the time for adding the oil phase is 30 to 40 minutes, and the particle size of the porous microspheres is 5 μm or less.
优选的，以重量份计，步骤（2）的具体方法如下：先将 1 份多孔微球、Preferably, in parts by weight, the specific method of step (2) is as follows: first mix 1 part of porous microspheres,
0.3～0.5 份 3-氨基酚、0.2～0.3 份乙酰乙酸乙酯加入 5～7 份无水乙醇中， 搅拌混匀，接着加入 0.3～0.5 份氯化锌，在氮气保护下，加热至回流，保温搅拌反应，反应结束后自然冷却至室温，加入 4～5 份质量浓度 36～38% 盐酸，搅拌混匀，过滤，水洗，干燥，即得所述的香豆素-多孔微球复合物。Add 0.3-0.5 parts of 3-aminophenol and 0.2-0.3 parts of ethyl acetoacetate into 5-7 parts of absolute ethanol, stir and mix well, then add 0.3-0.5 parts of zinc chloride, and heat to reflux under nitrogen protection. Insulate and stir for reaction. After the reaction is completed, cool naturally to room temperature, add 4 to 5 parts of hydrochloric acid with a mass concentration of 36 to 38%, stir and mix, filter, wash with water, and dry to obtain the coumarin-porous microsphere complex.
进一步优选的，反应时间为 6～8 小时。More preferably, the reaction time is 6-8 hours.
优选的，以重量份计，步骤（3）的具体方法如下：先将 1 份四（对羧基苯基）卟啉加入 4～5 份 N,N’-二甲基甲酰胺中，搅拌分散均匀，接着加入 1～2 份吡啶，搅拌混匀，然后在氮气保护下，边搅拌边加入 0.02～0.03 份四氯化钛，搅拌反应，后处理，即得所述的钛卟啉配合物。Preferably, in parts by weight, the specific method of step (3) is as follows: first add 1 part of tetrakis(p-carboxyphenyl)porphyrin to 4-5 parts of N,N'-dimethylformamide, stir and disperse evenly , followed by adding 1-2 parts of pyridine, stirring and mixing, and then adding 0.02-0.03 parts of titanium tetrachloride while stirring under the protection of nitrogen, stirring and reacting, and post-processing to obtain the titanium porphyrin complex.
进一步优选的，搅拌反应的工艺条件为：140～150℃搅拌反应 5～6 小时。Further preferably, the process condition of the stirring reaction is: stirring and reacting at 140-150°C for 5-6 hours.
进一步优选的，后处理的具体方法为：采用体积比 6：1 的氯仿-甲醇混合液进行硅胶柱层析分离，旋蒸除去溶剂，干燥即可。Further preferably, the specific post-treatment method is as follows: use a chloroform-methanol mixture with a volume ratio of 6:1 for silica gel column chromatography separation, rotary evaporation to remove the solvent, and then dry.
上述一种用于排水管道的常温原位修复材料的施工方法，先将 A 料和 B 料搅拌混匀，得到树脂母液，然后将软管利用树脂母液进行充分浸渍，并碾压至设计厚度，接着采用气体翻转设备对软管进行翻转施工，并利用空气压缩机将软管推动至待修复位置，向软管内持续充气使得软管与待修复管道紧密贴合，维持气压，发生固化反应，固化完成后拆除设备即可。The above-mentioned construction method for normal temperature in-situ repair materials for drainage pipes firstly mixes material A and material B to obtain a resin mother liquor, then fully impregnates the hose with the resin mother liquor, and rolls it to the designed thickness. Then use the gas turning equipment to turn over the hose, and use the air compressor to push the hose to the position to be repaired, and continue to inflate the hose to make the hose and the pipeline to be repaired closely, maintain the air pressure, and the curing reaction occurs. After the curing is completed, the device can be removed.
优选的，浸渍时间为 10～15 分钟，维持气压为 0.5～0.8MPa，固化反应时间为 20～30 分钟。Preferably, the immersion time is 10-15 minutes, the air pressure is maintained at 0.5-0.8 MPa, and the curing reaction time is 20-30 minutes.
有益效果Beneficial effect
与现有技术相比，本发明的有益效果是：Compared with prior art, the beneficial effect of the present invention is:
本发明提供了一种用于排水管道的常温原位修复材料，其包括 A 料和 B 料两部分，A 料是将酚醛环氧丙烯酸酯、双酚 A 环氧二丙烯酸酯和 2-甲基丙烯酸乙酯均匀混合而得，B 料是将 4-乙烯基苯甲醛、光引发剂 1173、偶氮二异丁腈、香豆素-多孔微球复合物、钛卟啉配合物、二氯甲烷、三氟乙酸均匀混合而得。在施工时，直接将 A 料和 B 料搅拌混匀，即配即用，使用方便，具有较高的机械性能和耐腐蚀性，对排水管道具有良好的修复性。本发明的优势如下：The invention provides a normal temperature in-situ repair material for drainage pipes, which includes two parts, material A and material B. Material A is a combination of novolac epoxy acrylate, bisphenol A epoxy diacrylate and 2-methyl Ethyl acrylate is uniformly mixed. Material B is 4-vinylbenzaldehyde, photoinitiator 1173, azobisisobutyronitrile, coumarin-porous microsphere complex, titanium porphyrin complex, dichloromethane , Trifluoroacetic acid obtained by uniform mixing. During construction, directly mix material A and material B, ready to use, easy to use, has high mechanical properties and corrosion resistance, and has good repairability for drainage pipes. The advantages of the present invention are as follows:
1、施工现场仅需要空气压缩机和气体翻转平台即可完成整个修复施工，无需额外的水源供应和材料牵拉设备，特别适用于施工现场难以直接到达的管道修复施工。1. The construction site only needs an air compressor and a gas turning platform to complete the entire repair construction, without additional water supply and material pulling equipment, especially suitable for pipeline repair construction that is difficult to reach directly on the construction site.
2、固化过程无需锅炉和光固化车辆，仅需要保持软管在固化过程中维持足够的气压，固化过程中仅需空气压缩机来维持压力。2. The curing process does not require boilers and light curing vehicles. It is only necessary to maintain sufficient air pressure in the hose during the curing process, and only an air compressor is needed to maintain the pressure during the curing process.
3、软管在现场进行浸渍压料，无需担心内衬软管在运输过程中发生固化，可根据现场的清淤情况合理及时安排施工时间。全面协调整体施工时间。3. The hose is impregnated and pressed on site, so there is no need to worry about the lining hose being solidified during transportation, and the construction time can be arranged in a reasonable and timely manner according to the dredging situation on site. Fully coordinate the overall construction time.
4、施工过程对于工程人员的要求较高，需要根据树脂的固化时间，合理安排整体施工流程，在树脂未发生固化前安装到位，对要求较为急迫的项目而言，施工整体过程可以得到直观的展示。4. The construction process has high requirements for engineering personnel. It is necessary to reasonably arrange the overall construction process according to the curing time of the resin, and install it in place before the resin is cured. For projects with more urgent requirements, the overall construction process can be intuitive. exhibit.
5、在 B 料中有两个关键组分，钛卟啉配合物和香豆素-多孔微球复合物。其中，钛卟啉配合物起到催化剂的作用，促进树脂聚合，由于其特殊的空间结构可促进环氧结构聚合枝化更为丰富，而枝化结构的形成有助于改善机械性能和耐腐蚀性；香豆素-多孔微球复合物起到填料的作用，均匀分散于体系中，进一步改善机械性能和耐腐蚀性。5. There are two key components in material B, titanium porphyrin complex and coumarin-porous microsphere complex. Among them, the titanium porphyrin complex acts as a catalyst to promote resin polymerization. Because of its special spatial structure, it can promote more abundant branching of epoxy structure polymerization, and the formation of branched structure helps to improve mechanical properties and corrosion resistance. Properties; the coumarin-porous microsphere composite acts as a filler and is uniformly dispersed in the system to further improve mechanical properties and corrosion resistance.
香豆素-多孔微球复合物的制备，是先以甲基丙烯酸缩水甘油酯和二甲基丙烯酸乙二醇酯为原料制备得到多孔微球，再将多孔微球、3-氨基酚、乙酰乙酸乙酯加入无水乙醇中，以氯化锌为催化剂，搅拌反应而得，在此过程中，生成的香豆素沉积在多孔微球表面或孔隙内，控制复合物粒径， 保证其在体系中均匀分散，同时借助多孔微球起到缓冲作用，改善机械性能和耐腐蚀性。The preparation of coumarin-porous microsphere composite is to prepare porous microspheres with glycidyl methacrylate and ethylene glycol dimethacrylate as raw materials, and then prepare porous microspheres, 3-aminophenol, acetyl Ethyl acetate is added to absolute ethanol, and zinc chloride is used as a catalyst to stir and react. During this process, the generated coumarin is deposited on the surface or pores of porous microspheres, and the particle size of the composite is controlled to ensure that it is in the It is uniformly dispersed in the system, and at the same time, it plays a buffer role with the help of porous microspheres to improve mechanical properties and corrosion resistance.
本发明的实施方式Embodiments of the present invention
下面将对本发明实施例中的技术方案进行清楚、完整地描述，显然， 所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。The following will clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only some of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without making creative efforts belong to the protection scope of the present invention.
实施例 1Example 1
一种用于排水管道的常温原位修复材料，其包括 A 料和 B 料两部分， A 料是将 100kg 酚醛环氧丙烯酸酯、80kg 双酚 A 环氧二丙烯酸酯、40kg 2- 甲基丙烯酸乙酯均匀混合而得；A normal temperature in-situ repair material for drainage pipes, which includes two parts, A material and B material, A material is 100kg novolac epoxy acrylate, 80kg bisphenol A epoxy diacrylate, 40kg Obtained by uniform mixing of 2- ethyl methacrylate;
B 料的制备方法如下：The preparation method of material B is as follows:
（1）先以甲基丙烯酸缩水甘油酯和二甲基丙烯酸乙二醇酯为原料制备多孔微球；(1) First prepare porous microspheres with glycidyl methacrylate and ethylene glycol dimethacrylate as raw materials;
（2）然后将多孔微球、3-氨基酚、乙酰乙酸乙酯加入无水乙醇中，以氯化锌为催化剂，搅拌反应，得到香豆素-多孔微球复合物；(2) Then add porous microspheres, 3-aminophenol, and ethyl acetoacetate into absolute ethanol, use zinc chloride as a catalyst, and stir for reaction to obtain a coumarin-porous microsphere composite;
（3）再以四（对羧基苯基）卟啉和四氯化钛为原料，氮气保护下反应得到钛卟啉配合物；(3) taking tetrakis(p-carboxyphenyl)porphyrin and titanium tetrachloride as raw materials, reacting under nitrogen protection to obtain titanium porphyrin complex;
（4）最后将 0.2kg 4-乙烯基苯甲醛、2kg 光引发剂 1173、1kg 偶氮二异丁腈、2kg 香豆素-多孔微球复合物、0.3kg 钛卟啉配合物、9kg 二氯甲烷、1kg 三氟乙酸均匀混合即得。(4) Finally, 0.2kg 4-vinylbenzaldehyde, 2kg photoinitiator 1173, 1kg azobisisobutyronitrile, 2kg coumarin-porous microsphere complex, 0.3kg titanium porphyrin complex, 9kg dichloro Mix methane and 1kg trifluoroacetic acid evenly.
步骤（1）的具体方法为：先将 60kg 甲基丙烯酸缩水甘油酯、35kg 二甲基丙烯酸乙二醇酯、45kg 邻苯二甲酸二乙酯和 2kg 过氧化苯甲酰搅拌混匀，得到油相；然后将 10kg 聚乙烯醇加入 1000kg 水中，搅拌混匀，得到水相；接着边搅拌边将油相缓慢匀速滴加至水相中，滴加完毕后，80℃和600r/min 条件下搅拌反应 3 小时，自然冷却至室温，离心，水洗，即得所述的多孔微球。The specific method of step (1) is: first stir and mix 60kg glycidyl methacrylate, 35kg ethylene glycol dimethacrylate, 45kg diethyl phthalate and 2kg benzoyl peroxide to obtain oil Phase; then 10kg Add polyvinyl alcohol into 1000kg of water, stir and mix to obtain the water phase; then slowly and uniformly drop the oil phase into the water phase while stirring, after the dropwise addition, stir and react at 80°C and 600r/min for 3 hours, naturally Cool to room temperature, centrifuge and wash with water to obtain the porous microspheres.
油相的滴加时间为 40 分钟，多孔微球的粒径为 5μm 以下。The dropping time of the oil phase was 40 minutes, and the particle size of the porous microspheres was below 5 μm.
步骤（2）的具体方法如下：先将 1kg 多孔微球、0.3kg3-氨基酚、0.3kg 乙酰乙酸乙酯加入 5kg 无水乙醇中，搅拌混匀，接着加入 0.5kg 氯化锌， 在氮气保护下，加热至回流，保温搅拌反应，反应结束后自然冷却至室温， 加入 4kg 质量浓度 38%盐酸，搅拌混匀，过滤，水洗，干燥，即得所述的香豆素-多孔微球复合物。The specific method of step (2) is as follows: first mix 1kg of porous microspheres, 0.3kg of 3-aminophenol, 0.3kg Add ethyl acetoacetate to 5kg absolute ethanol, stir and mix well, then add 0.5kg of zinc chloride, under the protection of nitrogen, heated to reflux, heat preservation and stirring reaction, naturally cooled to room temperature after the reaction, added 4kg of 38% hydrochloric acid in mass concentration, stirred and mixed, filtered, washed with water, dried to obtain the Coumarin-porous microsphere complex.
反应时间为 6 小时。The reaction time is 6 hours.
步骤（3）的具体方法如下：先将 1kg 四（对羧基苯基）卟啉加入 5kgN,N’-二甲基甲酰胺中，搅拌分散均匀，接着加入 1kg 吡啶，搅拌混匀，然后在氮气保护下，边搅拌边加入 0.03kg 四氯化钛，搅拌反应，后处理，即得所述的钛卟啉配合物。The specific method of step (3) is as follows: first add 1kg of tetrakis(p-carboxyphenyl)porphyrin to 5kg of N,N'-dimethylformamide, stir and disperse evenly, then add 1kg of pyridine, stir and mix, and then Under protection, add 0.03 kg of titanium tetrachloride while stirring, react with stirring, and perform post-treatment to obtain the titanium porphyrin complex.
搅拌反应的工艺条件为：140℃搅拌反应 6 小时。The process condition of stirring reaction is: 140°C stirring reaction for 6 hours.
后处理的具体方法为：采用体积比 6：1 的氯仿-甲醇混合液进行硅胶柱层析分离，旋蒸除去溶剂，干燥即可。The specific post-treatment method is as follows: use a chloroform-methanol mixture with a volume ratio of 6:1 for silica gel column chromatography, rotary evaporation to remove the solvent, and then dry.
实施例 2Example 2
一种用于排水管道的常温原位修复材料，其包括 A 料和 B 料两部分，A 料是将 100kg 酚醛环氧丙烯酸酯、100kg 双酚 A 环氧二丙烯酸酯、30kg 2- 甲基丙烯酸乙酯均匀混合而得；A normal temperature in-situ repair material for drainage pipes, which includes two parts, A material and B material, A material is 100kg novolac epoxy acrylate, 100kg bisphenol A epoxy diacrylate, 30kg Obtained by uniform mixing of 2- ethyl methacrylate;
B 料的制备方法如下：The preparation method of material B is as follows:
（1）先以甲基丙烯酸缩水甘油酯和二甲基丙烯酸乙二醇酯为原料制备多孔微球；(1) First prepare porous microspheres with glycidyl methacrylate and ethylene glycol dimethacrylate as raw materials;
（2）然后将多孔微球、3-氨基酚、乙酰乙酸乙酯加入无水乙醇中，以氯化锌为催化剂，搅拌反应，得到香豆素-多孔微球复合物；(2) Then add porous microspheres, 3-aminophenol, and ethyl acetoacetate into absolute ethanol, use zinc chloride as a catalyst, and stir for reaction to obtain a coumarin-porous microsphere composite;
（3）再以四（对羧基苯基）卟啉和四氯化钛为原料，氮气保护下反应得到钛卟啉配合物；(3) taking tetrakis(p-carboxyphenyl)porphyrin and titanium tetrachloride as raw materials, reacting under nitrogen protection to obtain titanium porphyrin complex;
（4）最后将 0.3kg 4-乙烯基苯甲醛、1kg 光引发剂 1173、2kg 偶氮二异丁腈、1kg 香豆素-多孔微球复合物、0.5kg 钛卟啉配合物、7kg 二氯甲烷、2kg 三氟乙酸均匀混合即得。(4) Finally, 0.3kg 4-vinylbenzaldehyde, 1kg photoinitiator 1173, 2kg azobisisobutyronitrile, 1kg coumarin-porous microsphere complex, 0.5kg titanium porphyrin complex, 7kg dichloro Mix methane and 2kg trifluoroacetic acid evenly.
步骤（1）的具体方法为：先将 50kg 甲基丙烯酸缩水甘油酯、45kg 二甲基丙烯酸乙二醇酯、35kg 邻苯二甲酸二乙酯和 3kg 过氧化苯甲酰搅拌混匀，得到油相；然后将 8kg 聚乙烯醇加入 1000kg 水中，搅拌混匀，得到水相；接着边搅拌边将油相缓慢匀速滴加至水相中，滴加完毕后， 85℃和500r/min 条件下搅拌反应 4 小时，自然冷却至室温，离心，水洗，即得所述的多孔微球。The specific method of step (1) is: first stir and mix 50kg glycidyl methacrylate, 45kg ethylene glycol dimethacrylate, 35kg diethyl phthalate and 3kg benzoyl peroxide to obtain oil Then add 8kg of polyvinyl alcohol into 1000kg of water, stir and mix to obtain the water phase; then add the oil phase to the water phase slowly and uniformly while stirring, after the addition is completed, stir at 85°C and 500r/min React for 4 hours, naturally cool to room temperature, centrifuge and wash with water to obtain the porous microspheres.
油相的滴加时间为 30 分钟，多孔微球的粒径为 5μm 以下。The dropping time of the oil phase was 30 minutes, and the particle size of the porous microspheres was below 5 μm.
步骤（2）的具体方法如下：先将 1kg 多孔微球、0.5kg3-氨基酚、0.2kg 乙酰乙酸乙酯加入 7kg 无水乙醇中，搅拌混匀，接着加入 0.3kg 氯化锌， 在氮气保护下，加热至回流，保温搅拌反应，反应结束后自然冷却至室温， 加入 5kg 质量浓度 36%盐酸，搅拌混匀，过滤，水洗，干燥，即得所述的香豆素-多孔微球复合物。The specific method of step (2) is as follows: first mix 1kg of porous microspheres, 0.5kg of 3-aminophenol, 0.2kg Add ethyl acetoacetate to 7kg of absolute ethanol, stir and mix well, then add 0.3kg of zinc chloride, under the protection of nitrogen, heated to reflux, heat preservation and stirring reaction, naturally cooled to room temperature after the reaction, added 5kg of 36% hydrochloric acid in mass concentration, stirred and mixed, filtered, washed with water, dried to obtain the Coumarin-porous microsphere complex.
反应时间为 8 小时。The reaction time is 8 hours.
步骤（3）的具体方法如下：先将 1kg 四（对羧基苯基）卟啉加入 4kgN,N’-二甲基甲酰胺中，搅拌分散均匀，接着加入 2kg 吡啶，搅拌混匀，然后在氮气保护下，边搅拌边加入 0.02kg 四氯化钛，搅拌反应，后处理，即得所述的钛卟啉配合物。The specific method of step (3) is as follows: first add 1kg of tetrakis(p-carboxyphenyl)porphyrin to 4kg of N,N'-dimethylformamide, stir and disperse evenly, then add 2kg of pyridine, stir and mix, and then Under protection, add 0.02 kg of titanium tetrachloride while stirring, react with stirring, and perform post-treatment to obtain the titanium porphyrin complex.
搅拌反应的工艺条件为： 150℃搅拌反应 5 小时。The process conditions of the stirring reaction are: 150°C stirring reaction for 5 hours.
后处理的具体方法为：采用体积比 6：1 的氯仿-甲醇混合液进行硅胶柱层析分离，旋蒸除去溶剂，干燥即可。The specific post-treatment method is as follows: use a chloroform-methanol mixture with a volume ratio of 6:1 for silica gel column chromatography, rotary evaporation to remove the solvent, and then dry.
实施例 3Example 3
一种用于排水管道的常温原位修复材料，其包括 A 料和 B 料两部分， A 料是将 100kg 酚醛环氧丙烯酸酯、90kg 双酚 A 环氧二丙烯酸酯、35kg 2- 甲基丙烯酸乙酯均匀混合而得；A normal temperature in-situ repair material for drainage pipes, which includes two parts A material and B material, A material is 100kg novolac epoxy acrylate, 90kg bisphenol A epoxy diacrylate, 35kg Obtained by uniform mixing of 2- ethyl methacrylate;
B 料的制备方法如下：The preparation method of material B is as follows:
（1）先以甲基丙烯酸缩水甘油酯和二甲基丙烯酸乙二醇酯为原料制备多孔微球；(1) First prepare porous microspheres with glycidyl methacrylate and ethylene glycol dimethacrylate as raw materials;
（2）然后将多孔微球、3-氨基酚、乙酰乙酸乙酯加入无水乙醇中，以氯化锌为催化剂，搅拌反应，得到香豆素-多孔微球复合物；(2) Then add porous microspheres, 3-aminophenol, and ethyl acetoacetate into absolute ethanol, use zinc chloride as a catalyst, and stir for reaction to obtain a coumarin-porous microsphere composite;
（3）再以四（对羧基苯基）卟啉和四氯化钛为原料，氮气保护下反应得到钛卟啉配合物；(3) taking tetrakis(p-carboxyphenyl)porphyrin and titanium tetrachloride as raw materials, reacting under nitrogen protection to obtain titanium porphyrin complex;
（4）最后将 0.25kg 4-乙烯基苯甲醛、1.5kg 光引发剂 1173、1.5kg 偶氮二异丁腈、1.5kg 香豆素-多孔微球复合物、0.4kg 钛卟啉配合物、8kg 二氯甲烷、1.5kg 三氟乙酸均匀混合即得。(4) Finally, 0.25kg 4-vinylbenzaldehyde, 1.5kg photoinitiator 1173, 1.5kg azobisisobutyronitrile, 1.5kg coumarin-porous microsphere complex, 0.4kg titanium porphyrin complex, Mix 8kg of dichloromethane and 1.5kg of trifluoroacetic acid evenly.
步骤（1）的具体方法为：先将 55kg 甲基丙烯酸缩水甘油酯、40kg 二甲基丙烯酸乙二醇酯、40kg 邻苯二甲酸二乙酯和 2.5kg 过氧化苯甲酰搅拌混匀，得到油相；然后将 9kg 聚乙烯醇加入 1000kg 水中，搅拌混匀，得到水相；接着边搅拌边将油相缓慢匀速滴加至水相中，滴加完毕后，82℃和600r/min 条件下搅拌反应 3.5 小时，自然冷却至室温，离心，水洗，即得所述的多孔微球。The specific method of step (1) is: first stir and mix 55kg glycidyl methacrylate, 40kg ethylene glycol dimethacrylate, 40kg diethyl phthalate and 2.5kg benzoyl peroxide to obtain oil phase; then add 9kg of polyvinyl alcohol into 1000kg of water, stir and mix well to obtain the water phase; then slowly add the oil phase to the water phase while stirring, and after the addition is completed, under the conditions of 82°C and 600r/min Stir the reaction for 3.5 hours, naturally cool to room temperature, centrifuge, and wash with water to obtain the porous microspheres.
油相的滴加时间为 35 分钟，多孔微球的粒径为 5μm 以下。The dropping time of the oil phase was 35 minutes, and the particle size of the porous microspheres was below 5 μm.
步骤（2）的具体方法如下：先将 1kg 多孔微球、0.4kg3-氨基酚、0.25kg 乙酰乙酸乙酯加入 6kg 无水乙醇中，搅拌混匀，接着加入 0.4kg 氯化锌，在氮气保护下，加热至回流，保温搅拌反应，反应结束后自然冷却至室温， 加入 4.5kg 质量浓度 37%盐酸，搅拌混匀，过滤，水洗，干燥，即得所述的香豆素-多孔微球复合物。The specific method of step (2) is as follows: first mix 1kg of porous microspheres, 0.4kg of 3-aminophenol, 0.25kg Add ethyl acetoacetate to 6kg of absolute ethanol, stir and mix well, then add 0.4kg zinc chloride, under nitrogen protection, heated to reflux, heat preservation and stirring reaction, naturally cooled to room temperature after the reaction, added 4.5kg mass concentration 37% hydrochloric acid, stirred and mixed, filtered, washed with water, dried to obtain the described coumarin-porous microsphere complexes.
反应时间为 7 小时。The reaction time is 7 hours.
步骤（3）的具体方法如下：先将1kg 四（对羧基苯基）卟啉加入4.5kgN,N’-二甲基甲酰胺中，搅拌分散均匀，接着加入 1.5kg 吡啶，搅拌混匀，然后在氮气保护下，边搅拌边加入 0.025kg 四氯化钛，搅拌反应，后处理，即得所述的钛卟啉配合物。The specific method of step (3) is as follows: first add 1kg of tetrakis(p-carboxyphenyl)porphyrin to 4.5kg of N,N’-dimethylformamide, stir and disperse evenly, then add 1.5kg of pyridine, stirred and mixed, and then under the protection of nitrogen, 0.025kg of titanium tetrachloride was added while stirring, stirred and reacted, and post-treated to obtain the titanium porphyrin complex.
搅拌反应的工艺条件为：145℃搅拌反应 5.5 小时。The process condition of the stirring reaction is: stirring reaction at 145°C for 5.5 hours.
后处理的具体方法为：采用体积比 6：1 的氯仿-甲醇混合液进行硅胶柱层析分离，旋蒸除去溶剂，干燥即可。The specific post-treatment method is as follows: use a chloroform-methanol mixture with a volume ratio of 6:1 for silica gel column chromatography, rotary evaporation to remove the solvent, and then dry.
对比例 1Comparative example 1
一种用于排水管道的常温原位修复材料，其包括 A 料和 B 料两部分， A 料是将 100kg 酚醛环氧丙烯酸酯、80kg 双酚 A 环氧二丙烯酸酯、40kg 2- 甲基丙烯酸乙酯均匀混合而得；A normal temperature in-situ repair material for drainage pipes, which includes two parts, A material and B material, A material is 100kg novolac epoxy acrylate, 80kg bisphenol A epoxy diacrylate, 40kg Obtained by uniform mixing of 2- ethyl methacrylate;
B 料的制备方法如下：The preparation method of material B is as follows:
（1）先以甲基丙烯酸缩水甘油酯和二甲基丙烯酸乙二醇酯为原料制备多孔微球；(1) First prepare porous microspheres with glycidyl methacrylate and ethylene glycol dimethacrylate as raw materials;
（2）然后以四（对羧基苯基）卟啉和四氯化钛为原料，氮气保护下反应得到钛卟啉配合物；(2) Then use tetrakis(p-carboxyphenyl)porphyrin and titanium tetrachloride as raw materials, react under nitrogen protection to obtain titanium porphyrin complex;
（3）最后将 0.2kg 4-乙烯基苯甲醛、2kg 光引发剂 1173、1kg 偶氮二异丁腈、2kg 多孔微球、0.3kg 钛卟啉配合物、9kg 二氯甲烷、1kg 三氟乙酸均匀混合即得。(3) Finally, 0.2kg 4-vinylbenzaldehyde, 2kg photoinitiator 1173, 1kg azobisisobutyronitrile, 2kg porous microspheres, 0.3kg titanium porphyrin complex, 9kg dichloromethane, 1kg trifluoroacetic acid Mix evenly and serve.
步骤（1）的具体方法为：先将 60kg 甲基丙烯酸缩水甘油酯、35kg 二甲基丙烯酸乙二醇酯、45kg 邻苯二甲酸二乙酯和 2kg 过氧化苯甲酰搅拌混匀，得到油相；然后将 10kg 聚乙烯醇加入 1000kg 水中，搅拌混匀，得到水相；接着边搅拌边将油相缓慢匀速滴加至水相中，滴加完毕后，80℃和600r/min 条件下搅拌反应 3 小时，自然冷却至室温，离心，水洗，即得所述的多孔微球。The specific method of step (1) is: first stir and mix 60kg glycidyl methacrylate, 35kg ethylene glycol dimethacrylate, 45kg diethyl phthalate and 2kg benzoyl peroxide to obtain oil Phase; then 10kg Add polyvinyl alcohol into 1000kg of water, stir and mix to obtain the water phase; then slowly and uniformly drop the oil phase into the water phase while stirring, after the dropwise addition, stir and react at 80°C and 600r/min for 3 hours, naturally Cool to room temperature, centrifuge and wash with water to obtain the porous microspheres.
油相的滴加时间为 40 分钟，多孔微球的粒径为 5μm 以下。The dropping time of the oil phase was 40 minutes, and the particle size of the porous microspheres was below 5 μm.
步骤（2）的具体方法如下：先将 1kg 四（对羧基苯基）卟啉加入 5kgN,N’The specific method of step (2) is as follows: first add 1kg tetrakis(p-carboxyphenyl)porphyrin to 5kgN,N’
-二甲基甲酰胺中，搅拌分散均匀，接着加入 1kg 吡啶，搅拌混匀，然后在氮气保护下，边搅拌边加入 0.03kg 四氯化钛，搅拌反应，后处理，即得所述的钛卟啉配合物。- in dimethylformamide, stir to disperse evenly, then add 1kg of pyridine, stir to mix, and then add 0.03kg of titanium tetrachloride was stirred and reacted, and post-treated to obtain the titanium porphyrin complex.
搅拌反应的工艺条件为：140℃搅拌反应 6 小时。The process condition of stirring reaction is: 140°C stirring reaction for 6 hours.
后处理的具体方法为：采用体积比 6：1 的氯仿-甲醇混合液进行硅胶柱层析分离，旋蒸除去溶剂，干燥即可。The specific post-treatment method is as follows: use a chloroform-methanol mixture with a volume ratio of 6:1 for silica gel column chromatography, rotary evaporation to remove the solvent, and then dry.
对比例 2Comparative example 2
一种用于排水管道的常温原位修复材料，其包括 A 料和 B 料两部分， A 料是将 100kg 酚醛环氧丙烯酸酯、80kg 双酚 A 环氧二丙烯酸酯、40kg 2- 甲基丙烯酸乙酯均匀混合而得；A normal temperature in-situ repair material for drainage pipes, which includes two parts, A material and B material, A material is 100kg novolac epoxy acrylate, 80kg bisphenol A epoxy diacrylate, 40kg Obtained by uniform mixing of 2- ethyl methacrylate;
B 料的制备方法如下：The preparation method of material B is as follows:
（1）再以四（对羧基苯基）卟啉和四氯化钛为原料，氮气保护下反应得到钛卟啉配合物；(1) Taking tetrakis(p-carboxyphenyl)porphyrin and titanium tetrachloride as raw materials, reacting under nitrogen protection to obtain titanium porphyrin complex;
（2）最后将 0.2kg 4-乙烯基苯甲醛、2kg 光引发剂 1173、1kg 偶氮二异丁腈、0.3kg 钛卟啉配合物、9kg 二氯甲烷、1kg 三氟乙酸均匀混合即得。(2) Finally, mix 0.2kg of 4-vinylbenzaldehyde, 2kg of photoinitiator 1173, 1kg of azobisisobutyronitrile, 0.3kg of titanium porphyrin complex, 9kg of methylene chloride, and 1kg of trifluoroacetic acid.
步骤（1）的具体方法如下：先将 1kg 四（对羧基苯基）卟啉加入 5kgN,N’-二甲基甲酰胺中，搅拌分散均匀，接着加入 1kg 吡啶，搅拌混匀，然后在氮气保护下，边搅拌边加入 0.03kg 四氯化钛，搅拌反应，后处理，即得所述的钛卟啉配合物。The specific method of step (1) is as follows: first add 1kg of tetrakis(p-carboxyphenyl)porphyrin to 5kg of N,N'-dimethylformamide, stir and disperse evenly, then add 1kg of pyridine, stir and mix, and then Under protection, add 0.03 kg of titanium tetrachloride while stirring, react with stirring, and perform post-treatment to obtain the titanium porphyrin complex.
搅拌反应的工艺条件为：140℃搅拌反应 6 小时。The process condition of stirring reaction is: 140°C stirring reaction for 6 hours.
后处理的具体方法为：采用体积比 6：1 的氯仿-甲醇混合液进行硅胶柱层析分离，旋蒸除去溶剂，干燥即可。The specific post-treatment method is as follows: use a chloroform-methanol mixture with a volume ratio of 6:1 for silica gel column chromatography, rotary evaporation to remove the solvent, and then dry.
对比例 3Comparative example 3
一种用于排水管道的常温原位修复材料，其包括 A 料和 B 料两部分， A 料是将 100kg 酚醛环氧丙烯酸酯、80kg 双酚 A 环氧二丙烯酸酯、40kg 2- 甲基丙烯酸乙酯均匀混合而得；A normal temperature in-situ repair material for drainage pipes, which includes two parts A material and B material, A material is 100kg novolac epoxy acrylate, 80kg bisphenol A epoxy diacrylate, 40kg Obtained by uniform mixing of 2- ethyl methacrylate;
B 料的制备方法如下：The preparation method of material B is as follows:
（1）先以甲基丙烯酸缩水甘油酯和二甲基丙烯酸乙二醇酯为原料制备多孔微球；(1) First prepare porous microspheres with glycidyl methacrylate and ethylene glycol dimethacrylate as raw materials;
（2）然后将多孔微球、3-氨基酚、乙酰乙酸乙酯加入无水乙醇中，以氯化锌为催化剂，搅拌反应，得到香豆素-多孔微球复合物；(2) Then add porous microspheres, 3-aminophenol, and ethyl acetoacetate into absolute ethanol, use zinc chloride as a catalyst, and stir for reaction to obtain a coumarin-porous microsphere composite;
（3）最后将 0.2kg 4-乙烯基苯甲醛、2kg 光引发剂 1173、1kg 偶氮二异丁腈、2kg 香豆素-多孔微球复合物、0.3kg 醋酸钴、9kg 二氯甲烷、1kg 三氟乙酸均匀混合即得。(3) Finally, 0.2kg 4-vinylbenzaldehyde, 2kg photoinitiator 1173, 1kg azobisisobutyronitrile, 2kg coumarin-porous microsphere complex, 0.3kg cobalt acetate, 9kg dichloromethane, 1kg Mix trifluoroacetic acid evenly.
步骤（1）的具体方法为：先将 60kg 甲基丙烯酸缩水甘油酯、35kg 二甲基丙烯酸乙二醇酯、45kg 邻苯二甲酸二乙酯和 2kg 过氧化苯甲酰搅拌混匀，得到油相；然后将 10kg 聚乙烯醇加入 1000kg 水中，搅拌混匀，得到水相；接着边搅拌边将油相缓慢匀速滴加至水相中，滴加完毕后，80℃和600r/min 条件下搅拌反应 3 小时，自然冷却至室温，离心，水洗，即得所述的多孔微球。The specific method of step (1) is: first stir and mix 60kg glycidyl methacrylate, 35kg ethylene glycol dimethacrylate, 45kg diethyl phthalate and 2kg benzoyl peroxide to obtain oil Phase; then 10kg Add polyvinyl alcohol into 1000kg of water, stir and mix to obtain the water phase; then slowly and uniformly drop the oil phase into the water phase while stirring, after the dropwise addition, stir and react at 80°C and 600r/min for 3 hours, the natural Cool to room temperature, centrifuge and wash with water to obtain the porous microspheres.
油相的滴加时间为 40 分钟，多孔微球的粒径为 5μm 以下。The dropping time of the oil phase was 40 minutes, and the particle size of the porous microspheres was below 5 μm.
步骤（2）的具体方法如下：先将 1kg 多孔微球、0.3kg3-氨基酚、0.3kg 乙酰乙酸乙酯加入 5kg 无水乙醇中，搅拌混匀，接着加入 0.5kg 氯化锌， 在氮气保护下，加热至回流，保温搅拌反应，反应结束后自然冷却至室温，加入 4kg 质量浓度 38%盐酸，搅拌混匀，过滤，水洗，干燥，即得所述的香豆素-多孔微球复合物。The specific method of step (2) is as follows: first mix 1kg of porous microspheres, 0.3kg of 3-aminophenol, 0.3kg Add ethyl acetoacetate to 5kg absolute ethanol, stir and mix well, then add 0.5kg of zinc chloride, under the protection of nitrogen, heated to reflux, heat preservation and stirring reaction, naturally cooled to room temperature after the reaction, added 4kg of 38% hydrochloric acid in mass concentration, stirred and mixed, filtered, washed with water, dried to obtain the Coumarin-porous microsphere complex.
反应时间为 6 小时。The reaction time is 6 hours.
分别将实施例 1～3 和对比例 1～3 所得修复材料用于排水管道的修复， 具体方法如下：先将 A 料和 B 料搅拌混匀，得到树脂母液，然后将软管利用树脂母液进行充分浸渍（浸渍时间 12 分钟），并碾压至设计厚度，接着采用气体翻转设备对软管进行翻转施工，并利用空气压缩机将软管推动至待修复位置，向软管内持续充气使得软管与待修复管道紧密贴合，维持气压 0.7Ma，发生固化反应（固化反应时间为 25 分钟），固化完成后拆除设备即可。The repair materials obtained in Examples 1-3 and Comparative Examples 1-3 were respectively used for the repair of drainage pipes. The specific method is as follows: First, stir and mix materials A and B to obtain a resin mother liquor, and then use the resin mother liquor to clean the hose. Fully impregnate (impregnation time is 12 minutes), and roll to the design thickness, then use the air turning equipment to turn over the hose, and use the air compressor to push the hose to the position to be repaired, and continue to inflate the hose to make the soft The tube fits closely with the pipeline to be repaired to maintain air pressure 0.7Ma, the curing reaction occurs (the curing reaction time is 25 minutes), and the device can be removed after the curing is completed.
参考 ASTM F1216 进行机械性能和耐腐蚀性考察，结果见表 1 和表 2。在进行耐腐蚀性考察时，在 23℃条件下，分别利用腐蚀性物质接触一个月，设置空白对照，一个月后再次检测机械性能，空白对照组的挠曲强度为 148.7MPa。Refer to ASTM F1216 for mechanical properties and corrosion resistance, the results are shown in Table 1 and Table 2. When conducting corrosion resistance investigations, under the condition of 23°C, the corrosive substances were used to contact for one month, and a blank control was set up, and the mechanical properties were tested again after one month. The flexural strength of the blank control group was 148.7 MPa.
表 1. 机械性能考察 Table 1. Mechanical properties investigation
挠曲强度（MPa）Flexural strength (MPa)
实施例 1Example 1 121.2121.2
实施例 2Example 2 113.4113.4
实施例 3Example 3 108.9108.9
对比例 1Comparative example 1 99.699.6
对比例 2Comparative example 2 83.483.4
对比例 3Comparative example 3 89.789.7
表 2. 耐腐蚀性考察Table 2. Corrosion resistance investigation
 the 挠曲强度（MPa）, 质量浓度 10%硫酸溶液Flexural strength (MPa), Mass concentration 10% sulfuric acid solution 挠曲强度（MPa）,自来水Flexural strength (MPa), tap water 挠曲强度（MPa）,汽油Flexural strength (MPa), gasoline
实施例 1Example 1 125.3125.3 128.1128.1 128.6128.6
实施例 2Example 2 119.8119.8 123.6123.6 130.1130.1
实施例 3Example 3 121.6121.6 125.3125.3 135.1135.1
对比例 1Comparative example 1 104.5104.5 105.2105.2 106.3106.3
对比例 2Comparative example 2 92.292.2 95.895.8 96.296.2
对比例 3Comparative example 3 97.197.1 98.098.0 98.998.9
由表 1 和表 2 可知，利用实施例 1～3 所得修复材料进行排水管道的修复，机械性能和耐腐蚀性优异。且优于对比例 1-3 的性能。It can be seen from Table 1 and Table 2 that the repair materials obtained in Examples 1 to 3 are used for the repair of drainage pipes, and the mechanical properties and corrosion resistance are excellent. And better than the performance of Comparative Examples 1-3.
对于本领域技术人员而言，显然本发明不限于上述示范性实施例的细节，而且在不背离本发明的精神或基本特征的情况下，能够以其他的具体形式实现本发明。因此，无论从哪一点来看，均应将实施例看作是示范性的，而且是非限制性的，本发明的范围由所附权利要求而不是上述说明限定，因此旨在将落在权利要求的等同要件的含义和范围内的所有变化囊括在本发明内。It will be apparent to those skilled in the art that the invention is not limited to the details of the above-described exemplary embodiments, but that the invention can be embodied in other specific forms without departing from the spirit or essential characteristics of the invention. Accordingly, the embodiments should be regarded in all points of view as exemplary and not restrictive, the scope of the invention being defined by the appended claims rather than the foregoing description, and it is therefore intended that the scope of the invention be defined by the appended claims rather than by the foregoing description. All changes within the meaning and range of equivalents of the elements are embraced in the present invention.
此外，应当理解，虽然本说明书按照实施方式加以描述，但并非每个实施方式仅包含一个独立的技术方案，说明书的这种叙述方式仅仅是为清楚起见，本领域技术人员应当将说明书作为一个整体，各实施例中的技术方案也可以经适当组合，形成本领域技术人员可以理解的其他实施方式。In addition, it should be understood that although this specification is described according to implementation modes, not each implementation mode only contains an independent technical solution, and this description in the specification is only for clarity, and those skilled in the art should take the specification as a whole , the technical solutions in the various embodiments can also be properly combined to form other implementations that can be understood by those skilled in the art.

Claims (10)

  1. 一种用于排水管道的常温原位修复材料，其特征在于，其包括 A 料和 B 料两部分，以重量份计，A 料是将 100 份酚醛环氧丙烯酸酯、80～100 份双酚 A 环氧二丙烯酸酯、30～40 份 2-甲基丙烯酸乙酯均匀混合而得；A normal temperature in-situ repair material for drainage pipes, characterized in that it includes two parts, A material and B material, in parts by weight, A material is 100 parts of novolac epoxy acrylate, 80-100 parts of bisphenol A Obtained by uniformly mixing epoxy diacrylate and 30-40 parts of 2-ethyl methacrylate;
    所述 B 料的制备方法如下：The preparation method of the B material is as follows:
    （1）先以甲基丙烯酸缩水甘油酯和二甲基丙烯酸乙二醇酯为原料制备多孔微球；(1) First prepare porous microspheres with glycidyl methacrylate and ethylene glycol dimethacrylate as raw materials;
    （2）然后将多孔微球、3-氨基酚、乙酰乙酸乙酯加入无水乙醇中，以氯化锌为催化剂，搅拌反应，得到香豆素-多孔微球复合物；(2) Then add porous microspheres, 3-aminophenol, and ethyl acetoacetate into absolute ethanol, use zinc chloride as a catalyst, and stir for reaction to obtain a coumarin-porous microsphere composite;
    （3）再以四（对羧基苯基）卟啉和四氯化钛为原料，氮气保护下反应得到钛卟啉配合物；(3) taking tetrakis(p-carboxyphenyl)porphyrin and titanium tetrachloride as raw materials, reacting under nitrogen protection to obtain titanium porphyrin complex;
    （4）最后将 0.2～0.3 份 4-乙烯基苯甲醛、1～2 份光引发剂 1173、1～2 份偶氮二异丁腈、1～2 份香豆素-多孔微球复合物、0.3～0.5 份钛卟啉配合物、7～9 份二氯甲烷、1～2 份三氟乙酸均匀混合即得。(4) Finally, 0.2-0.3 parts of 4-vinylbenzaldehyde, 1-2 parts of photoinitiator 1173, 1-2 parts of azobisisobutyronitrile, 1-2 parts of coumarin-porous microsphere complex, 0.3-0.5 parts of titanium porphyrin complex, 7-9 parts of dichloromethane, and 1-2 parts of trifluoroacetic acid are uniformly mixed.
  2. 根据权利要求 1 所述的一种用于排水管道的常温原位修复材料，其特征在于，以重量份计，步骤（1）的具体方法为：先将 50～60 份甲基丙烯酸缩水甘油酯、35～45 份二甲基丙烯酸乙二醇酯、35～45 份邻苯二甲酸二乙酯和 2～3 份过氧化苯甲酰搅拌混匀，得到油相；然后将 8～10 份聚乙烯醇加入 1000 份水中，搅拌混匀，得到水相；接着边搅拌边将油相缓慢匀速滴加至水相中，滴加完毕后，80～85℃和 500～600r/min 条件下搅拌反应 3～4 小时，自然冷却至室温，离心，水洗，即得所述的多孔微球。A normal temperature in-situ repair material for drainage pipes according to claim 1, characterized in that, in parts by weight, the specific method of step (1) is: first add 50-60 parts of glycidyl methacrylate , 35 to 45 parts of ethylene glycol dimethacrylate, 35 to 45 parts of diethyl phthalate and 2 to 3 parts of benzoyl peroxide were stirred and mixed to obtain an oil phase; then 8 to 10 parts of poly Add vinyl alcohol to 1000 parts of water, stir and mix to obtain the water phase; then slowly and uniformly drop the oil phase into the water phase while stirring. After 3-4 hours, naturally cool to room temperature, centrifuge, and wash with water to obtain the porous microspheres.
  3. 根据权利要求 1 所述的一种用于排水管道的常温原位修复材料，其特征在于，油相的滴加时间为 30～40 分钟，多孔微球的粒径为 5μm 以下。A normal temperature in-situ repair material for drainage pipes according to claim 1, characterized in that the dripping time of the oil phase is After 30-40 minutes, the particle size of the porous microspheres is below 5 μm.
  4. 根据权利要求 1 所述的一种用于排水管道的常温原位修复材料，其特征在于，以重量份计，步骤（2）的具体方法如下：先将 1 份多孔微球、0.3～0.5 份 3-氨基酚、0.2～0.3 份乙酰乙酸乙酯加入 5～7 份无水乙醇中， 搅拌混匀，接着加入 0.3～0.5 份氯化锌，在氮气保护下，加热至回流，保温搅拌反应，反应结束后自然冷却至室温，加入 4～5 份质量浓度 36～38% 盐酸，搅拌混匀，过滤，水洗，干燥，即得所述的香豆素-多孔微球复合物。A normal temperature in-situ repair material for drainage pipes according to claim 1, characterized in that, in parts by weight, the specific method of step (2) is as follows: first mix 1 part of porous microspheres, 0.3-0.5 parts Add 3-aminophenol, 0.2-0.3 parts of ethyl acetoacetate to 5-7 parts of absolute ethanol, Stir and mix well, then add 0.3~0.5 parts of zinc chloride, under the protection of nitrogen, heat to reflux, keep warm and stir to react, after the reaction is finished, cool to room temperature naturally, add 4~5 parts of hydrochloric acid with a mass concentration of 36~38%, stir and mix Homogenize, filter, wash with water, and dry to obtain the coumarin-porous microsphere complex.
  5. 根据权利要求 4 所述的一种用于排水管道的常温原位修复材料，其特征在于，反应时间为 6～8 小时。A normal temperature in-situ repair material for drainage pipes according to claim 4, characterized in that the reaction time is 6-8 hours.
  6. 根据权利要求 1 所述的一种用于排水管道的常温原位修复材料，其特征在于，以重量份计，步骤（3）的具体方法如下：先将 1 份四（对羧基苯基）卟啉加入 4～5 份 N,N’-二甲基甲酰胺中，搅拌分散均匀，接着加入1～2 份吡啶，搅拌混匀，然后在氮气保护下，边搅拌边加入 0.02～0.03 份四氯化钛，搅拌反应，后处理，即得所述的钛卟啉配合物。A normal temperature in-situ repair material for drainage pipes according to claim 1, characterized in that, in parts by weight, the specific method of step (3) is as follows: first, 1 part of tetrakis (p-carboxyphenyl) porphyrin Add 4-5 parts of N,N'-dimethylformamide to morphine, stir and disperse evenly, then add 1-2 parts of pyridine, stir and mix well, then add 0.02-0.03 parts of tetrachloromethane while stirring under the protection of nitrogen Titanium, stirring reaction, post-treatment, that is, the titanium porphyrin complex.
  7. 根据权利要求 6 所述的一种用于排水管道的常温原位修复材料，其特征在于，搅拌反应的工艺条件为：140～150℃搅拌反应 5～6 小时。A normal temperature in-situ repair material for drainage pipes according to claim 6, characterized in that the process conditions of the stirring reaction are: stirring reaction at 140-150°C for 5-6 hours.
  8. 根据权利要求 6 所述的一种用于排水管道的常温原位修复材料，其特征在于，后处理的具体方法为：采用体积比 6：1 的氯仿-甲醇混合液进行硅胶柱层析分离，旋蒸除去溶剂，干燥即可。A normal temperature in-situ repair material for drainage pipes according to claim 6, characterized in that the specific post-treatment method is: using a chloroform-methanol mixture with a volume ratio of 6:1 for silica gel column chromatography separation, The solvent was removed by rotary evaporation and dried.
  9. 一种权利要求 1～8 中任一项所述用于排水管道的常温原位修复材料的施工方法，其特征在于，先将 A 料和 B 料搅拌混匀，得到树脂母液， 然后将软管利用树脂母液进行充分浸渍，并碾压至设计厚度，接着采用气体翻转设备对软管进行翻转施工，并利用空气压缩机将软管推动至待修复位置，向软管内持续充气使得软管与待修复管道紧密贴合，维持气压，发生固化反应，固化完成后拆除设备即可。A construction method for the normal temperature in-situ repair material for drainage pipes according to any one of claims 1 to 8, characterized in that firstly mixing material A and material B to obtain a resin mother liquor, and then putting the hose Use the resin mother liquor to fully impregnate and roll to the design thickness, then use the air turning equipment to turn the hose over, and use the air compressor to push the hose to the position to be repaired, and continue to inflate the hose so that the hose and The pipelines to be repaired are tightly bonded, the air pressure is maintained, and the curing reaction occurs. After the curing is completed, the equipment can be removed.
  10. 根据权利要求 9 所述的用于排水管道的常温原位修复材料的施工方法，其特征在于，一种浸渍时间为 10～15 分钟，维持气压为 0.5～0.8MPa， 固化反应时间为 20～30 分钟。The construction method of the normal temperature in-situ repair material for drainage pipes according to claim 9, characterized in that the immersion time is 10-15 minutes, the maintenance air pressure is 0.5-0.8MPa, and the curing reaction time is 20-30 minute.
PCT/CN2022/111363 2021-07-27 2022-08-10 Normal-temperature in-situ repair material for drainage pipeline, and construction method therefor WO2023006123A1 (en)

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