CN101096584A - High-strength water-based itaconic acid epoxide resin grouting material and preparation method thereof - Google Patents
High-strength water-based itaconic acid epoxide resin grouting material and preparation method thereof Download PDFInfo
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- CN101096584A CN101096584A CNA2007100287590A CN200710028759A CN101096584A CN 101096584 A CN101096584 A CN 101096584A CN A2007100287590 A CNA2007100287590 A CN A2007100287590A CN 200710028759 A CN200710028759 A CN 200710028759A CN 101096584 A CN101096584 A CN 101096584A
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Abstract
The invention discloses a high-strength grouting material of aqueous itaconic acid epoxy ester resin and making method, which comprises the following parts: 30-80% neutralized aqueous itaconic acid epoxy ester resin, 10-70% diluent, 0-100% water, 1-10% crosslinking agent, 0-0.1% storing stabilizer, 0-0.5% deoxidizer, 1-4% initiator, 0.5-4% accelerant and 0-2% boosting accelerant. The invention reduces the water content of grouting material to add the content of polymerisable component and increase the mechanic strength of the material, which is fit for kinds of engineering reinforcing and water shutoff course to make high-strength aqueous epoxy cement slurry through blending with cement slurry.
Description
Technical field
The present invention relates to injection material, be specifically related to a kind of high-strength water-based itaconic acid epoxide resin grouting material and preparation method thereof.
Background technology
Application number is 200410027818.9, the Chinese invention patent application documents that name is called " a kind of method for making of novel aqueous epoxide resin grouting material " disclose a kind of novel aqueous epoxide resin grouting material, this invention is by methylene-succinic acid and Resins, epoxy reaction, on the Resins, epoxy molecular skeleton, introduce carboxyl, utilize in the neutralizing agent then and salify, thereby realize Water-borne modification of epoxy resins, two keys of Yin Ruing simultaneously, under redox system, generate gel by free radical polymerization.This invention preferably resolves Water-borne modification of epoxy resins, and successful preparation can substitute third coagulate, the novel environment friendly injection material of water shutoff material such as acrylate.
But still there is the following problem in this injection material that provides in this invention:
The first, the selection of solubility promoter.Used propyl carbinol, pimelinketone, acetone, ethylene glycol monobutyl ether, propylene glycol monobutyl ether etc. to make solubility promoter during preparation methylene-succinic acid epoxy ester resin, wherein pure and mild ketone volatility is strong, smell is more unpleasant, and ethylene glycol monobutyl ether, propylene glycol monobutyl ether etc. are owing to have injury to ban use of abroad to people's reproductive system, thus the use of these solvents this be unfavorable for the environmental requirement of material and workmen's safety.
The second, the employing of neutralizing agent.In resin and the time adopt neutralizing agents such as ammoniacal liquor, diethylamine and trolamine, such neutralizing agent only participates in salify, in the solidification process of slurry material, do not participate in curing reaction, and the consistency of these micromolecular addings and resin body is not fine, therefore the physical strength of induration is not high, the induration instability that forms is decomposed in the high water of saltiness easily.
Three, the selection of curing system.When in this patent, preparing aqueous epoxy resin grouting material, solidifying agent adopts water-soluble initiation reduction system, this kind solidifying agent can cause slurries rapidly and solidifies having under the condition of water, but stopping of chain takes place in the process of chainpropagation easily, the molecular weight of the polymkeric substance that generates is less, therefore causes the bulk strength of material not high.
Four, the induration physical strength is low.The ultimate compression strength of this material has only 0.65-4.5Mpa, can not be used for reinforcing in the grouting field, can only be used for water blockoff, and this has also limited this kind water-base epoxy in the grouting Application for Field.
Summary of the invention
In order to overcome the existing above-mentioned shortcoming and defect of prior art, further expand the waterborne epoxy resin applications scope, the invention provides a kind of content that reduces water, increase the content of polymerizable components, improved the physical strength of material, make its reinforcing that can be applied to various engineerings, water blockoff antiseepage, and can prepare the high-strength water-based itaconic acid epoxide resin grouting material of high-intensity water-base epoxy sand-cement slurry with the sand-cement slurry blend.The present invention also provides the preparation method of this high-strength water-based itaconic acid epoxide resin grouting material simultaneously.
High-strength water-based itaconic acid epoxide resin grouting material of the present invention comprises following components in weight portions:
The water-based itaconic acid epoxy ester resin 30-80 part that had neutralized
Thinner 10-70 part
Water 0-100 part
Linking agent 1-10 part
Shelf-stable agent 0-0.1 part
Oxygen scavenger 0.1-0.5 part
Initiator 1-4 part
Promotor 0.5-4 part
Secondary accelerator 0.1-2 part.
For better realization the present invention, high-strength water-based itaconic acid epoxide resin grouting material of the present invention also can comprise the component of following weight part: toughner 10-30 part.
Described toughner can be made by following method: add polyisocyanates in filling the container of nitrogen, drip polyether glycol (within 1-2 hour, adding) then, heat 2.5-3h down at 50-70 ℃, drip the excessive monomer that contains two keys and hydroxyl at 70-80 ℃ then and carry out end-blocking as end-capping reagent, reaction 2-3h obtains toughner;
Wherein, described polyisocyanates comprises TDI (tolylene diisocyanate), MDI ('-diphenylmethane diisocyanate), emulsifying water MDI ('-diphenylmethane diisocyanate of emulsifying water), HDI (hexamethylene diisocyanate); Described polyether glycol comprises the liquid pfpe of molecular weight between 100-10000; The consumption mol ratio of polyisocyanates and polyether glycol is 1.5-2.5: 1;
The described monomer that contains two keys and hydroxyl comprises hydroxyethyl methylacrylate, Rocryl 410, allyl alcohol, Hydroxyethyl acrylate, Propylene glycol monoacrylate or lactic acid allyl ester; The liquid pfpe of molecular weight between 100-10000 comprises N204, N210, N220, N303 or N330;
Described thinner comprises following double bond containing monomer: methyl methacrylate, hydroxyethyl methylacrylate, Rocryl 410, butyl methacrylate, Hydroxyethyl acrylate, vinyl acetate, 1, the 3-butylene glycol dimethacrylate, 1, the 4-butylene glycol dimethacrylate, neopentylglycol dimethacrylate, trimethylolpropane trimethacrylate, the tripropylene glycol dimethacrylate, the dipropylene glycol dimethacrylate, the propylene glycol dimethacrylate, Ethylene glycol dimethacrylate, the Diethylene Glycol dimethacrylate, the triethylene glycol dimethacrylate, the TEG dimethacrylate, pentaerythritol acrylate trimethyl, tetramethylolmethane tetramethyl-acrylate, 1, the 6-hexanediol dimethacrylate, glyceral methacrylate, glycidyl methacrylate, allyl methacrylate(AMA), isobornyl methacrylate, polyoxyethylene glycol (200) dimethacrylate, polyoxyethylene glycol (400) dimethacrylate, diallyl phthalate, the ethoxyquin bisphenol a diacrylate, methacrylic acid-2-phenoxy ethyl, trimethylolpropane allyl ether, the Diethylene Glycol divinyl ether, the triethylene glycol divinyl ether, 1,4-hydroxymethyl-cyclohexane divinyl ether, 1,4-butyleneglycol divinyl ether, trimethylolpropane tris vinyl ether or ethylene liquid paracril.
Described linking agent comprises trimethylolpropane trimethacrylate, tripropylene glycol dimethacrylate, dipropylene glycol dimethacrylate, propylene glycol dimethacrylate, pentaerythritol acrylate trimethyl, tetramethylolmethane tetramethyl-acrylate or trimethylolpropane tris vinyl ether.
Described shelf-stable agent comprises disodium EDTA, phenylbenzene-N-nitrosamine, nitrosophenol, Dyhard RU 100, benzoquinones, anthraquinone or oxalic acid.
Described oxygen scavenger comprises toluenesulfinic acid or trimethylolpropane allyl ether.
Described initiator comprises benzoyl peroxide, cyclohexanone peroxide, methylethyl ketone peroxide, dicumyl peroxide, the phenylformic acid peroxidation tert-butyl ester, t-butyl hydrogen peroxide, asccharin-1,2,3,4 tetrahydroquinolines, asccharin-N, N-dimethyl-p-toluidine, tertbutyl peroxide, isopropyl benzene hydroperoxide, 9-boron dicyclo (3,3,1) nonane, tri butyl boron or triethyl-boron.
Described promotor comprises N, and accelerine, dimethyl are to monomethylaniline, diphenylmethyl hydrazides, pyrodin, phenylhydrazine, pyrazoles, N nitrosodiphenyl amine, sad ketone, propylene diamine, ferrocene, zinc chloride, trolamine, cobalt naphthenate, cobalt iso-octoate, naphthoic acid cobalt or tetrahydroquinoline.
Described secondary accelerator comprises asccharin, phthalimide, triphenylphosphine, xitix, triphenylphosphine or pyrodin.
The described water-based itaconic acid epoxy ester resin that had neutralized can be made by following method: nitrogen is being housed, in the container of whipping appts and thermometer, add methylene-succinic acid and solubility promoter, add catalyzer and stopper, when being warming up to 80-90 ℃, splash into Resins, epoxy (within 1-2h, adding), adding back maintenance thermostat temperature is 110-115 ℃, reaction 2-3h, stopped reaction when surveying acid number and reaching 80-200 milligram/gram, be cooled to 55-65 ℃, add active neutralizing agent and be neutralized to pH value between 7.0-7.5, fully stir, add thinner then and be diluted to viscosity, get the water-based itaconic acid epoxy ester resin that had neutralized at 20-200mPa.s;
Wherein, described active neutralizing agent is to comprise following two keys and the amino organic bases of containing: methacrylic acid N, N-dimethylamino ethyl ester, methacrylic acid N, N-diethylamino ethyl ester or 2-(diethylamide) ethanol vinyl ether; Described solubility promoter comprises methyl methacrylate, hydroxyethyl methylacrylate, Rocryl 410, allyl alcohol, Hydroxyethyl acrylate, Propylene glycol monoacrylate or vinyl acetate; Described catalyzer comprises triethylamine, N, accelerine or benzyltriethylammoinium chloride; Described stopper comprises phenol, Resorcinol, p-tert-butylphenol or p-ten.-butylcatechol; Described thinner comprises following double bond containing monomer: methyl methacrylate, hydroxyethyl methylacrylate, Rocryl 410, butyl methacrylate, Hydroxyethyl acrylate, vinyl acetate, 1, the 3-butylene glycol dimethacrylate, 1, the 4-butylene glycol dimethacrylate, neopentylglycol dimethacrylate, trimethylolpropane trimethacrylate, the tripropylene glycol dimethacrylate, the dipropylene glycol dimethacrylate, the propylene glycol dimethacrylate, Ethylene glycol dimethacrylate, the Diethylene Glycol dimethacrylate, the triethylene glycol dimethacrylate, the TEG dimethacrylate, pentaerythritol acrylate trimethyl, tetramethylolmethane tetramethyl-acrylate, 1, the 6-hexanediol dimethacrylate, glyceral methacrylate, glycidyl methacrylate, allyl methacrylate(AMA), isobornyl methacrylate, polyoxyethylene glycol (200) dimethacrylate, polyoxyethylene glycol (400) dimethacrylate, diallyl phthalate, the ethoxyquin bisphenol a diacrylate, methacrylic acid-2-phenoxy ethyl, trimethylolpropane allyl ether, the Diethylene Glycol divinyl ether, the triethylene glycol divinyl ether, 1,4-hydroxymethyl-cyclohexane divinyl ether, 1,4-butyleneglycol divinyl ether, trimethylolpropane tris vinyl ether or ethylene liquid paracril; The mol ratio of described methylene-succinic acid and Resins, epoxy is 2-2.5: 1, and solubility promoter is the 10%-100% of Resins, epoxy quality, and catalyzer is the 0.2%-4% of Resins, epoxy quality, and stopper is the 0.1%-3% of Resins, epoxy quality.
Preparation method provided by the present invention may further comprise the steps:
The preparation of the water-based itaconic acid epoxy ester resin that (1) had neutralized
In the container that nitrogen, whipping appts and thermometer are housed, add methylene-succinic acid and solubility promoter, add catalyzer and stopper, when being warming up to 80-90 ℃, splash into Resins, epoxy (in 1～2 hour, adding), adding the back, to keep thermostat temperature be 110～115 ℃, reaction stopped reaction when surveying acid number and reach 80-200 milligram/gram;
Be cooled to 55-65 ℃, add active neutralizing agent and be neutralized to pH value between 7.0-7.5, fully stir, add thinner then and be diluted to viscosity, get the water-soluble methylene-succinic acid that had neutralized at 20-200mPa.s
Epoxy ester resin;
(2) preparation of toughner
In filling the container of nitrogen, add polyisocyanates, drip polyether glycol (adding within 1-2 hour) then, heat 2.5-3h down at 50-70 ℃, drip the excessive monomer that contains two keys and hydroxyl at 70-80 ℃ then and carry out end-blocking as end-capping reagent, reaction 2-3h obtains toughner;
(3) raw material of following ratio is mixed promptly get high-strength water-based itaconic acid epoxy ester resin injection material, the weight part proportioning of each raw material is as follows:
The water-based itaconic acid of neutral epoxy ester resin 30-80 part of step (1) gained
Toughner 10-30 part of step (2) gained
Thinner 10-70 part
Water 0-100 part
Linking agent 1-10 part
Shelf-stable agent 0-0.1 part
Oxygen scavenger 0-0.5 part
Initiator 1-4 part
Promotor 0.5-4 part
Secondary accelerator 0-2 part;
Active neutralizing agent described in the described step (1) comprises following two keys and the amino organic bases of containing: methacrylic acid N, N-dimethylamino ethyl ester, methacrylic acid N, N-diethylamino ethyl ester or 2-(diethylamide) ethanol vinyl ether; Solubility promoter comprises methyl methacrylate, hydroxyethyl methylacrylate, Rocryl 410, allyl alcohol, Hydroxyethyl acrylate, Propylene glycol monoacrylate or vinyl acetate; Described catalyzer comprises triethylamine, N, accelerine or benzyltriethylammoinium chloride; Described stopper comprises phenol, Resorcinol, p-tert-butylphenol or p-ten.-butylcatechol; The described thinner of step (1) comprises following double bond containing monomer: methyl methacrylate, hydroxyethyl methylacrylate, Rocryl 410, butyl methacrylate, Hydroxyethyl acrylate, vinyl acetate, 1, the 3-butylene glycol dimethacrylate, 1, the 4-butylene glycol dimethacrylate, neopentylglycol dimethacrylate, trimethylolpropane trimethacrylate, the tripropylene glycol dimethacrylate, the dipropylene glycol dimethacrylate, the propylene glycol dimethacrylate, Ethylene glycol dimethacrylate, the Diethylene Glycol dimethacrylate, the triethylene glycol dimethacrylate, the TEG dimethacrylate, pentaerythritol acrylate trimethyl, tetramethylolmethane tetramethyl-acrylate, 1, the 6-hexanediol dimethacrylate, glyceral methacrylate, glycidyl methacrylate, allyl methacrylate(AMA), isobornyl methacrylate, polyoxyethylene glycol (200) dimethacrylate, polyoxyethylene glycol (400) dimethacrylate, diallyl phthalate, the ethoxyquin bisphenol a diacrylate, methacrylic acid-2-phenoxy ethyl, trimethylolpropane allyl ether, the Diethylene Glycol divinyl ether, the triethylene glycol divinyl ether, 1,4-hydroxymethyl-cyclohexane divinyl ether, 1,4-butyleneglycol divinyl ether, trimethylolpropane tris vinyl ether or ethylene liquid paracril; The mol ratio of described methylene-succinic acid and Resins, epoxy is 2-2.5: 1, and solubility promoter is the 10%-100% of Resins, epoxy quality, and catalyzer is the 0.2%-4% of Resins, epoxy quality, and stopper is the 0.1%-3% of Resins, epoxy quality.
Polyisocyanates described in the described step (2) comprises TDI, MDI, emulsifying water MDI, HDI; Described polyether glycol comprises the liquid pfpe of molecular weight between 100-10000; Wherein the liquid pfpe of molecular weight between 100-10000 comprises N204, N210, N220, N303 or N330; The consumption mol ratio of polyisocyanates and polyether glycol is 1.5-2.5: 1.
The described monomer that contains two keys and hydroxyl comprises hydroxyethyl methylacrylate, Rocryl 410, allyl alcohol, Hydroxyethyl acrylate, Propylene glycol monoacrylate or lactic acid allyl ester.
The described thinner of step (3) comprises following double bond containing monomer: methyl methacrylate, hydroxyethyl methylacrylate, Rocryl 410, butyl methacrylate, Hydroxyethyl acrylate, vinyl acetate, 1, the 3-butylene glycol dimethacrylate, 1, the 4-butylene glycol dimethacrylate, neopentylglycol dimethacrylate, trimethylolpropane trimethacrylate, the tripropylene glycol dimethacrylate, the dipropylene glycol dimethacrylate, the propylene glycol dimethacrylate, Ethylene glycol dimethacrylate, the Diethylene Glycol dimethacrylate, the triethylene glycol dimethacrylate, the TEG dimethacrylate, pentaerythritol acrylate trimethyl, tetramethylolmethane tetramethyl-acrylate, 1, the 6-hexanediol dimethacrylate, glyceral methacrylate, glycidyl methacrylate, allyl methacrylate(AMA), isobornyl methacrylate, polyoxyethylene glycol (200) dimethacrylate, polyoxyethylene glycol (400) dimethacrylate, diallyl phthalate, the ethoxyquin bisphenol a diacrylate, methacrylic acid-2-phenoxy ethyl, trimethylolpropane allyl ether, the Diethylene Glycol divinyl ether, the triethylene glycol divinyl ether, 1,4-hydroxymethyl-cyclohexane divinyl ether, 1,4-butyleneglycol divinyl ether, trimethylolpropane tris vinyl ether or ethylene liquid paracril;
Described linking agent comprises trimethylolpropane trimethacrylate, tripropylene glycol dimethacrylate, dipropylene glycol dimethacrylate, propylene glycol dimethacrylate, pentaerythritol acrylate trimethyl, tetramethylolmethane tetramethyl-acrylate or trimethylolpropane tris vinyl ether;
Described shelf-stable agent comprises disodium EDTA, phenylbenzene-N-nitrosamine, nitrosophenol, Dyhard RU 100, benzoquinones, anthraquinone or oxalic acid;
Described oxygen scavenger comprises toluenesulfinic acid or trimethylolpropane allyl ether;
Described initiator comprises benzoyl peroxide, cyclohexanone peroxide, methylethyl ketone peroxide, dicumyl peroxide, the phenylformic acid peroxidation tert-butyl ester, t-butyl hydrogen peroxide, asccharin-1,2,3,4 tetrahydroquinolines, asccharin-N, N-dimethyl-p-toluidine, tertbutyl peroxide, isopropyl benzene hydroperoxide, 9-boron dicyclo (3,3,1) nonane, tri butyl boron or triethyl-boron;
Described promotor comprises N, and accelerine, dimethyl are to monomethylaniline, diphenylmethyl hydrazides, pyrodin, phenylhydrazine, pyrazoles, N nitrosodiphenyl amine, sad ketone, propylene diamine, ferrocene, zinc chloride, trolamine, cobalt naphthenate, cobalt iso-octoate, naphthoic acid cobalt or tetrahydroquinoline;
Described secondary accelerator comprises asccharin, phthalimide, triphenylphosphine, xitix, triphenylphosphine or pyrodin.
High-strength water-based itaconic acid epoxide resin grouting material provided by the invention is compared with existing injection material, has the following advantages:
(1) injection material of the present invention has reduced the content of water, increased the content of polymerizable components, improved the physical strength of material, made its reinforcing that can be applied to various engineerings, water blockoff antiseepage, and can prepare high-intensity water-base epoxy sand-cement slurry with the sand-cement slurry blend;
(2) injection material of the present invention has been cancelled the poisonous nonactive solubility promoter that pollution is arranged, and adopts the response type solubility promoter, thereby makes material environmental protection more; Neutralizing agent adopts the organic bases that contains two keys not only not change the material good water-solubility, and has improved the intensity of material greatly, has reduced the unstable of material; The adding of toughner has reduced the surfaces of tacky phenomenon of vinyl material in addition, has strengthened the toughness of material.
(3) injection material provided by the invention can solidify having under the condition of water, the viscosity of slurries can be regulated between 10-200mP.s, can pour into the fine cracks of 0.02cm, can regulate between several seconds to several hours working life, needed engineering time when the rapid curing in the time of both can satisfying water blockoff also can be satisfied reinforcing.The physical strength of slurry material induration will be higher than the Chinese invention patent 200410027818.9 disclosed strengths of materials far away among the present invention, can be used for the reinforcing of cement concrete and the impervious leakage-stopping of various engineerings.The material induration of different instances prescription physical strength after a week is as shown in the table:
Table one: the mechanical property of different ingredients
| The prescription number | ?1 | ?2 | ?3 | ?4 | ?6 |
| Neutral resin/g | ?100 | ?100 | ?100 | ?100 | ?100 |
| Thinner/g | ?50 | ?70 | ?60 | ?70 | ?70 |
Embodiment
In order to further specify the present invention, specific embodiments more of the present invention and Comparative Examples below are provided, understand the present invention to help further, but protection scope of the present invention is not limited in this.
Embodiment 1:
The preparation of the water-based itaconic acid epoxy ester resin that (1) had neutralized
In the 1000ml four-hole boiling flask of nitrogen, whipping appts and thermometer is housed, add 139.2g methylene-succinic acid and 120g hydroxyethyl methylacrylate, add benzyl triethyl ammonium ammonia chloride 1.52g and 0.42g Resorcinol, during heat temperature raising to 85 ℃, gradation adds 200gE-51 Resins, epoxy, adding back maintenance thermostat temperature is 110 ℃, and reaction 2h surveys acid number and reaches 80 milligrams/stopped reaction when restraining.
Reduce temperature to 60 ℃, add DMAM and neutralize, fully stir, add the dilution of 200g methyl methacrylate then, fully stir water-based itaconic acid epoxide resin.
(2) preparation of epoxide resin grouting material
Get above resin 100g, add cobalt iso-octoate 1.2g, add 6g tripropylene glycol dimethacrylate, add methylethyl ketone peroxide 2.6g, the mixed injection material that evenly is.
This material cured is after one week, and the physical strength of induration is as follows: ultimate compression strength 80.42MPa, shearing resistance 9.52MPa, bonding strength 3.70MPa.
Embodiment 2:
The preparation of the water-based itaconic acid epoxy ester resin that (1) had neutralized
In the 1000ml four-hole boiling flask of nitrogen, whipping appts and thermometer is housed, add 100g methylene-succinic acid and 50g hydroxyethyl methylacrylate, add benzyl triethyl ammonium ammonia chloride 1.09g and 0.30g Resorcinol, during heat temperature raising to 85 ℃, gradation adds 143.7gE-51 Resins, epoxy, adding back maintenance thermostat temperature is 115 ℃, and reaction 3h surveys acid number and reaches 200 milligrams/stopped reaction when restraining.
Reduce temperature to 60 ℃, add DMAM and neutralize, fully stir, add 140gMMA and 70gHEMA dilution then, add then water 140g fully stir water-based itaconic acid epoxide resin.
(2) preparation of epoxide resin grouting material
Get above resin 100g, add cobalt iso-octoate 1.8g, add 6g tripropylene glycol dimethacrylate, add methylethyl ketone peroxide 3.6g, mix and evenly be injection material of the present invention.
This material cured is after one week, and the physical strength of induration is as follows: ultimate compression strength 58.17MPa, shearing resistance 1.27MPa.
Embodiment 3:
The preparation of the water-based itaconic acid epoxy ester resin that (1) had neutralized
In the 1000ml four-hole boiling flask of nitrogen, whipping appts and thermometer is housed, add 139.2g methylene-succinic acid and 120g hydroxyethyl methylacrylate, add benzyl triethyl ammonium ammonia chloride 1.52g and 0.42g Resorcinol, during heat temperature raising to 85 ℃, gradation adds 200gE-51 Resins, epoxy, adding back maintenance thermostat temperature is 112 ℃, and reaction 2.5h surveys acid number and reaches 150 milligrams/stopped reaction when restraining.
Reduce temperature to 60 ℃, add DMAM and neutralize, fully stir, add the 220gMMA dilution then, add again water 63g fully stir water-based itaconic acid epoxide resin.
(2) toughner is synthetic
In the 500ml four-hole boiling flask of nitrogen, whipping appts and thermometer is housed, add 87gTDI, drip the N204 polyether glycol under the room temperature, drip the complete 50 ℃ of heating 3h that are warming up to, drip HEMA50g at 70 ℃ then, reaction 3h obtains toughner.
(3) preparation of epoxide resin grouting material
Get above resin 100g, add toughner 20g, cobalt iso-octoate 2.7g adds 6g tripropylene glycol dimethacrylate, adds methylethyl ketone peroxide 5.4g, the mixed injection material that evenly is.
This material cured is after one week, and the physical strength of induration is as follows: ultimate compression strength 64.70MPa, shearing resistance 4.44MPa, bonding strength 0.82MPa.
Embodiment 4:
The preparation of the water-based itaconic acid epoxy ester resin that (1) had neutralized
In the 1000ml four-hole boiling flask of nitrogen, whipping appts and thermometer is housed, add 139.2g methylene-succinic acid and 200g methyl methacrylate, add triethylamine 1.52g and 0.60g p-ten.-butylcatechol, during heat temperature raising to 85 ℃, gradation adds 232gE-44 Resins, epoxy, adding back maintenance thermostat temperature is 110-115 ℃, and reaction 2h surveys acid number and reaches 80 milligrams/stopped reaction when restraining.
Reduce temperature to 60 ℃, add DMAM and neutralize, fully stir, add the 120gMMA dilution then, add again water 80g fully stir water-based itaconic acid epoxide resin.
(2) toughner is synthetic
In the 500ml four-hole boiling flask of nitrogen, whipping appts and thermometer is housed, add 87gTDI, drip the N204 polyether glycol under the room temperature, drip the complete 50 ℃ of heating 2.5-3h that are warming up to, drip HEA50g at 70 ℃ then, reaction 2-3h obtains this plasticized modifier.
(3) preparation of epoxide resin grouting material
Get above resin 100g, add toughner 20g, trolamine 2.0g adds 6g tripropylene glycol dimethacrylate, adds peroxy-disulfuric acid amine 3.4g, the mixed injection material that evenly is.
This material cured is after one week, and the physical strength of induration is as follows: ultimate compression strength 55.4MPa, shearing resistance 3.87MPa, bonding strength 0.56MPa.
Embodiment 5:
The preparation of the water-based itaconic acid epoxy ester resin that (1) had neutralized
In the 1000ml four-hole boiling flask of nitrogen, whipping appts and thermometer is housed, add 139.2g methylene-succinic acid and 200g methyl methacrylate, add triethylamine 1.52g and 0.42g Resorcinol, during heat temperature raising to 85 ℃, gradation adds 200gE-51 Resins, epoxy, adding back maintenance thermostat temperature is 115 ℃, and reaction 2h surveys acid number and reaches 100 milligrams/stopped reaction when restraining.
Reduce temperature to 60 ℃, add DMAM and neutralize, fully stir, add the 120gMMA dilution then, add again water 40g fully stir water-based itaconic acid epoxide resin.
(2) toughner is synthetic
In the 500ml four-hole boiling flask of nitrogen, whipping appts and thermometer is housed, add 87gTDI, drip N210 polyether glycol 250g under the room temperature, drip the complete 50 ℃ of heating 2.5h that are warming up to, drip HEMA50g at 70 ℃ then, reaction 2h obtains toughner.
(3) preparation of epoxide resin grouting material
Get above resin 100g, add toughner 20g, N, accelerine 2.7g adds 6g tripropylene glycol dimethacrylate, adds BP05.4g, mixes evenly promptly.
This material cured is after one week, and the physical strength of induration is as follows: ultimate compression strength 58.47MPa, shearing resistance 5.14MPa, bonding strength 0.84MPa
Embodiment 6
Active neutralizing agent methacrylic acid N, N-diethylamino ethyl ester, solubility promoter are used pyrodin, secondary accelerator triphenylphosphine with trimethylolpropane allyl ether, initiator with cyclohexanone peroxide, promotor with nitrosophenol, oxygen scavenger with dipropylene glycol dimethacrylate, shelf-stable agent with N220, the monomer allyl alcohol that contains two keys and hydroxyl, linking agent with emulsifying water MDI, polyether glycol with butyl methacrylate, polyisocyanates with Resorcinol, thinner with benzyltriethylammoinium chloride, stopper with allyl alcohol, catalyzer; Other conditions are with embodiment 3.
Embodiment 7
Active neutralizing agent 2-(diethylamide) ethanol vinyl ether, the solubility promoter Propylene glycol monoacrylate, the catalyzer triethylamine, N, accelerine, the stopper p-tert-butylphenol, thinner triethylene glycol dimethacrylate, polyisocyanates HDI, polyether glycol N303, the monomer Propylene glycol monoacrylate that contains two keys and hydroxyl, linking agent propylene glycol dimethacrylate, shelf-stable agent Dyhard RU 100, the oxygen scavenger toluenesulfinic acid, the initiator t-butyl hydrogen peroxide, promotor is used pyrazoles, the secondary accelerator triphenylphosphine, other conditions are with embodiment 4.
Embodiment 8
Active neutralizing agent methacrylic acid N, N-diethylamino ethyl ester, solubility promoter are used trolamine, secondary accelerator pyrodin with oxalic acid, initiator with triethyl-boron, promotor with trimethylolpropane tris vinyl ether, shelf-stable agent with N330, linking agent with vinyl acetate, thinner diallyl phthalate, polyether glycol, and other conditions are with embodiment 5.
Claims (9)
1, a kind of high-strength water-based itaconic acid epoxide resin grouting material is characterized in that, comprises following components in weight portions:
The water-based itaconic acid epoxy ester resin 30-80 part that had neutralized
Thinner 10-70 part
Water 0-100 part
Linking agent 1-10 part
Shelf-stable agent 0-0.1 part
Oxygen scavenger 0-0.5 part
Initiator 1-4 part
Promotor 0.5-4 part
Secondary accelerator 0-2 part.
2, a kind of high-strength water-based itaconic acid epoxide resin grouting material according to claim 1 is characterized in that, also comprises the component of following weight part: toughner 10-30 part.
3, a kind of high-strength water-based itaconic acid epoxide resin grouting material according to claim 2 is characterized in that, described toughner is to be made by following method:
Add polyisocyanates in filling the container of nitrogen, drip polyether glycol then, heat 2.5-3h down at 50-70 ℃, drip the excessive monomer that contains two keys and hydroxyl at 70-80 ℃ then and carry out end-blocking as end-capping reagent, reaction 2-3h obtains toughner;
Wherein, described polyisocyanates comprises TDI, MDI, emulsifying water MDI, HDI; Described polyether glycol comprises the liquid pfpe of molecular weight between 100-10000; The mol ratio of the consumption of polyisocyanates and polyether glycol is 1.5-2.5: 1;
The described monomer that contains two keys and hydroxyl comprises hydroxyethyl methylacrylate, Rocryl 410, allyl alcohol, Hydroxyethyl acrylate, Propylene glycol monoacrylate or lactic acid allyl ester; The liquid pfpe of described molecular weight between 100-10000 comprises N204, N210, N220, N303 or N330.
4, a kind of high-strength water-based itaconic acid epoxide resin grouting material according to claim 1 is characterized in that, the described water-based itaconic acid epoxy ester resin that had neutralized is to be made by following method:
In the container that nitrogen, whipping appts and thermometer are housed, add methylene-succinic acid and solubility promoter, add catalyzer and stopper, be warming up to 80-90 ℃, splash into Resins, epoxy, adding back maintenance thermostat temperature is 110-115 ℃, reaction stopped reaction when surveying acid number and reach 80-200 milligram/gram, be cooled to 55-65 ℃, add active neutralizing agent and be neutralized to pH value between 7.0-7.5, fully stir, add thinner then and be diluted to viscosity, get the water-based itaconic acid epoxy ester resin that had neutralized at 20-200mPa.s.
5, according to the described a kind of high-strength water-based itaconic acid epoxide resin grouting material of claim 4, it is characterized in that, described active neutralizing agent is to comprise following two keys and the amino organic bases of containing: methacrylic acid N, N-dimethylamino ethyl ester, methacrylic acid N, N-diethylamino ethyl ester or 2-(diethylamide) ethanol vinyl ether;
Described solubility promoter comprises methyl methacrylate, hydroxyethyl methylacrylate, Rocryl 410, allyl alcohol, Hydroxyethyl acrylate, Propylene glycol monoacrylate or vinyl acetate;
Described catalyzer comprises triethylamine, N, accelerine or benzyltriethylammoinium chloride;
Described stopper comprises phenol, Resorcinol, p-tert-butylphenol or p-ten.-butylcatechol;
Described thinner comprises following double bond containing monomer: methyl methacrylate, hydroxyethyl methylacrylate, Rocryl 410, butyl methacrylate, Hydroxyethyl acrylate, vinyl acetate, 1, the 3-butylene glycol dimethacrylate, 1, the 4-butylene glycol dimethacrylate, neopentylglycol dimethacrylate, trimethylolpropane trimethacrylate, the tripropylene glycol dimethacrylate, the dipropylene glycol dimethacrylate, the propylene glycol dimethacrylate, Ethylene glycol dimethacrylate, the Diethylene Glycol dimethacrylate, the triethylene glycol dimethacrylate, the TEG dimethacrylate, pentaerythritol acrylate trimethyl, tetramethylolmethane tetramethyl-acrylate, 1, the 6-hexanediol dimethacrylate, glyceral methacrylate, glycidyl methacrylate, allyl methacrylate(AMA), isobornyl methacrylate, polyoxyethylene glycol (200) dimethacrylate, polyoxyethylene glycol (400) dimethacrylate, diallyl phthalate, the ethoxyquin bisphenol a diacrylate, methacrylic acid-2-phenoxy ethyl, trimethylolpropane allyl ether, the Diethylene Glycol divinyl ether, the triethylene glycol divinyl ether, 1,4-hydroxymethyl-cyclohexane divinyl ether, 1,4-butyleneglycol divinyl ether, trimethylolpropane tris vinyl ether or ethylene liquid paracril;
The mol ratio of described methylene-succinic acid and Resins, epoxy is 2-2.5: 1, and solubility promoter is the 10%-100% of Resins, epoxy quality, and catalyzer is the 0.2%-4% of Resins, epoxy quality, and stopper is the 0.1%-3% of Resins, epoxy quality.
6, according to the described a kind of high-strength water-based itaconic acid epoxide resin grouting material of claim 1, it is characterized in that described thinner comprises double bond containing monomer;
Described linking agent comprises trimethylolpropane trimethacrylate, tripropylene glycol dimethacrylate, dipropylene glycol dimethacrylate, propylene glycol dimethacrylate, pentaerythritol acrylate trimethyl, tetramethylolmethane tetramethyl-acrylate or trimethylolpropane tris vinyl ether;
Described shelf-stable agent comprises disodium EDTA, phenylbenzene-N-nitrosamine, nitrosophenol, Dyhard RU 100, benzoquinones, anthraquinone or oxalic acid;
Described oxygen scavenger comprises toluenesulfinic acid or trimethylolpropane allyl ether;
Described initiator comprises benzoyl peroxide, cyclohexanone peroxide, methylethyl ketone peroxide, dicumyl peroxide, the phenylformic acid peroxidation tert-butyl ester, t-butyl hydrogen peroxide, asccharin-1,2,3,4 tetrahydroquinolines, asccharin-N, N-dimethyl-p-toluidine, tertbutyl peroxide, isopropyl benzene hydroperoxide, 9-boron dicyclo (3,3,1) nonane, tri butyl boron or triethyl-boron;
Described promotor comprises N, and accelerine, dimethyl are to monomethylaniline, diphenylmethyl hydrazides, pyrodin, phenylhydrazine, pyrazoles, N nitrosodiphenyl amine, sad ketone, propylene diamine, ferrocene, zinc chloride, trolamine, cobalt naphthenate, cobalt iso-octoate, naphthoic acid cobalt or tetrahydroquinoline;
Described secondary accelerator comprises asccharin, phthalimide, triphenylphosphine, xitix, triphenylphosphine or pyrodin.
7, according to the described a kind of high-strength water-based itaconic acid epoxide resin grouting material of claim 6, it is characterized in that, described double bond containing monomer comprises methyl methacrylate, hydroxyethyl methylacrylate, Rocryl 410, butyl methacrylate, Hydroxyethyl acrylate, vinyl acetate, 1, the 3-butylene glycol dimethacrylate, 1, the 4-butylene glycol dimethacrylate, neopentylglycol dimethacrylate, trimethylolpropane trimethacrylate, the tripropylene glycol dimethacrylate, the dipropylene glycol dimethacrylate, the propylene glycol dimethacrylate, Ethylene glycol dimethacrylate, the Diethylene Glycol dimethacrylate, the triethylene glycol dimethacrylate, the TEG dimethacrylate, pentaerythritol acrylate trimethyl, tetramethylolmethane tetramethyl-acrylate, 1, the 6-hexanediol dimethacrylate, glyceral methacrylate, glycidyl methacrylate, allyl methacrylate(AMA), isobornyl methacrylate, polyoxyethylene glycol (200) dimethacrylate, polyoxyethylene glycol (400) dimethacrylate, diallyl phthalate, the ethoxyquin bisphenol a diacrylate, methacrylic acid-2-phenoxy ethyl, trimethylolpropane allyl ether, the Diethylene Glycol divinyl ether, the triethylene glycol divinyl ether, 1,4-hydroxymethyl-cyclohexane divinyl ether, 1,4-butyleneglycol divinyl ether, trimethylolpropane tris vinyl ether or ethylene liquid paracril.
8, the preparation method of the described a kind of high-strength water-based itaconic acid epoxide resin grouting material of claim 1 may further comprise the steps:
The preparation of the water-based itaconic acid epoxy ester resin that (1) had neutralized
In the container that nitrogen, whipping appts and thermometer are housed, add methylene-succinic acid and solubility promoter, add catalyzer and stopper, when being warming up to 80-90 ℃, splash into Resins, epoxy, adding the back, to keep thermostat temperature be 110～115 ℃, reaction stopped reaction when surveying acid number and reach 80-200 milligram/gram, the water-based itaconic acid epoxy ester resin that had been neutralized;
Be cooled to 55-65 ℃, add active neutralizing agent and be neutralized to pH value between 7.0-7.5, fully stir, add thinner then and be diluted to viscosity, get the water-based itaconic acid epoxy ester resin that had neutralized at 20-200mPa.s;
(2) preparation of toughner
Add a certain amount of polyisocyanates in filling the flask of nitrogen, drip polyether glycol then, heat 2.5-3h down at 50-70 ℃, drip the excessive monomer that contains two keys and hydroxyl at 70-80 ℃ then and carry out end-blocking as end-capping reagent, reaction 2-3h obtains toughner;
(3) raw material of following ratio is mixed promptly get high-strength water-based itaconic acid epoxy ester resin injection material, the weight part proportioning of each raw material is as follows:
The water-based itaconic acid epoxide resin of neutral 30-80 part of step (1) gained
Toughner 10-30 part of step (2) gained
Thinner 10-70 part
Water 0-100 part
Linking agent 1-10 part
Shelf-stable agent 0-0.1 part
Oxygen scavenger 0-0.5 part
Initiator 1-4 part
Promotor 0.5-4 part
Secondary accelerator 0-2 part.
9, according to the preparation method of the described a kind of high-strength water-based itaconic acid epoxide resin grouting material of claim 8, it is characterized in that,
In the described step (1):
Described active neutralizing agent comprises following two keys and the amino organic bases of containing: methacrylic acid N, N-dimethylamino ethyl ester, methacrylic acid N, N-diethylamino ethyl ester or 2-(diethylamide) ethanol vinyl ether;
Described solubility promoter comprises methyl methacrylate, hydroxyethyl methylacrylate, Rocryl 410, allyl alcohol, Hydroxyethyl acrylate, Propylene glycol monoacrylate or vinyl acetate;
Described catalyzer comprises triethylamine, N, accelerine or benzyltriethylammoinium chloride; Described stopper comprises phenol, Resorcinol, p-tert-butylphenol or p-ten.-butylcatechol;
Described thinner comprises following double bond containing monomer: methyl methacrylate, hydroxyethyl methylacrylate, Rocryl 410, butyl methacrylate, Hydroxyethyl acrylate, vinyl acetate, 1, the 3-butylene glycol dimethacrylate, 1, the 4-butylene glycol dimethacrylate, neopentylglycol dimethacrylate, trimethylolpropane trimethacrylate, the tripropylene glycol dimethacrylate, the dipropylene glycol dimethacrylate, the propylene glycol dimethacrylate, Ethylene glycol dimethacrylate, the Diethylene Glycol dimethacrylate, the triethylene glycol dimethacrylate, the TEG dimethacrylate, pentaerythritol acrylate trimethyl, tetramethylolmethane tetramethyl-acrylate, 1, the 6-hexanediol dimethacrylate, glyceral methacrylate, glycidyl methacrylate, allyl methacrylate(AMA), isobornyl methacrylate, polyoxyethylene glycol (200) dimethacrylate, polyoxyethylene glycol (400) dimethacrylate, diallyl phthalate, the ethoxyquin bisphenol a diacrylate, methacrylic acid-2-phenoxy ethyl, trimethylolpropane allyl ether, the Diethylene Glycol divinyl ether, the triethylene glycol divinyl ether, 1,4-hydroxymethyl-cyclohexane divinyl ether, 1,4-butyleneglycol divinyl ether, trimethylolpropane tris vinyl ether or ethylene liquid paracril;
The mol ratio of described methylene-succinic acid and Resins, epoxy is 2-2.5: 1, and solubility promoter is the 10%-100% of Resins, epoxy quality, and catalyzer is the 0.2%-4% of Resins, epoxy quality, and stopper is the 0.1%-3% of Resins, epoxy quality;
In the described step (2):
Described polyisocyanates comprises TDI, MDI, emulsifying water MDI, HDI;
Described polyether glycol comprises molecular weight following liquid pfpe: N204, N210, N220, N303 or N330 between 100-10000;
The mol ratio of the consumption of described polyisocyanates and polyether glycol is 1.5-2.5: 1;
The described monomer that contains two keys and hydroxyl comprises hydroxyethyl methylacrylate, Rocryl 410, allyl alcohol, Hydroxyethyl acrylate, Propylene glycol monoacrylate or lactic acid allyl ester;
In the described step (3):
Described thinner comprises following double bond containing monomer: methyl methacrylate, hydroxyethyl methylacrylate, Rocryl 410, butyl methacrylate, Hydroxyethyl acrylate, vinyl acetate, 1, the 3-butylene glycol dimethacrylate, 1, the 4-butylene glycol dimethacrylate, neopentylglycol dimethacrylate, trimethylolpropane trimethacrylate, the tripropylene glycol dimethacrylate, the dipropylene glycol dimethacrylate, the propylene glycol dimethacrylate, Ethylene glycol dimethacrylate, the Diethylene Glycol dimethacrylate, the triethylene glycol dimethacrylate, the TEG dimethacrylate, pentaerythritol acrylate trimethyl, tetramethylolmethane tetramethyl-acrylate, 1, the 6-hexanediol dimethacrylate, glyceral methacrylate, glycidyl methacrylate, allyl methacrylate(AMA), isobornyl methacrylate, polyoxyethylene glycol (200) dimethacrylate, polyoxyethylene glycol (400) dimethacrylate, diallyl phthalate, the ethoxyquin bisphenol a diacrylate, methacrylic acid-2-phenoxy ethyl, trimethylolpropane allyl ether, the Diethylene Glycol divinyl ether, the triethylene glycol divinyl ether, 1,4-hydroxymethyl-cyclohexane divinyl ether, 1,4-butyleneglycol divinyl ether, trimethylolpropane tris vinyl ether or ethylene liquid paracril;
Described linking agent comprises trimethylolpropane trimethacrylate, tripropylene glycol dimethacrylate, dipropylene glycol dimethacrylate, propylene glycol dimethacrylate, pentaerythritol acrylate trimethyl, tetramethylolmethane tetramethyl-acrylate or trimethylolpropane tris vinyl ether;
Described shelf-stable agent comprises disodium EDTA, phenylbenzene-N-nitrosamine, nitrosophenol, Dyhard RU 100, benzoquinones, anthraquinone or oxalic acid;
Described oxygen scavenger comprises toluenesulfinic acid or trimethylolpropane allyl ether;
Described initiator comprises benzoyl peroxide, cyclohexanone peroxide, methylethyl ketone peroxide, dicumyl peroxide, the phenylformic acid peroxidation tert-butyl ester, t-butyl hydrogen peroxide, asccharin-1,2,3,4 tetrahydroquinolines, asccharin-N, N-dimethyl-p-toluidine, tertbutyl peroxide, isopropyl benzene hydroperoxide, 9-boron dicyclo (3,3,1) nonane, tri butyl boron or triethyl-boron;
Described promotor comprises N, and accelerine, dimethyl are to monomethylaniline, diphenylmethyl hydrazides, pyrodin, phenylhydrazine, pyrazoles, N nitrosodiphenyl amine, sad ketone, propylene diamine, ferrocene, zinc chloride, trolamine, cobalt naphthenate, cobalt iso-octoate or naphthoic acid cobalt or tetrahydroquinoline;
Described secondary accelerator comprises asccharin, phthalimide, triphenylphosphine, xitix, triphenylphosphine or pyrodin.
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