CN100355816C - Mesh subaqueous patching material of interpenetrating polymer of epoxy/polyurethane, preparing process and application - Google Patents
Mesh subaqueous patching material of interpenetrating polymer of epoxy/polyurethane, preparing process and application Download PDFInfo
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- CN100355816C CN100355816C CNB2005100184260A CN200510018426A CN100355816C CN 100355816 C CN100355816 C CN 100355816C CN B2005100184260 A CNB2005100184260 A CN B2005100184260A CN 200510018426 A CN200510018426 A CN 200510018426A CN 100355816 C CN100355816 C CN 100355816C
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- 239000000463 material Substances 0.000 title claims abstract description 74
- 239000004593 Epoxy Substances 0.000 title claims abstract description 38
- 229920000642 polymer Polymers 0.000 title claims abstract description 37
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 32
- 239000004814 polyurethane Substances 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims description 11
- 230000008569 process Effects 0.000 title description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 34
- 239000003822 epoxy resin Substances 0.000 claims abstract description 32
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 32
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000002360 preparation method Methods 0.000 claims abstract description 19
- 239000003085 diluting agent Substances 0.000 claims abstract description 4
- 239000003999 initiator Substances 0.000 claims description 18
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 11
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 11
- CMEWLCATCRTSGF-UHFFFAOYSA-N N,N-dimethyl-4-nitrosoaniline Chemical compound CN(C)C1=CC=C(N=O)C=C1 CMEWLCATCRTSGF-UHFFFAOYSA-N 0.000 claims description 11
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 11
- -1 hexanol amine Chemical class 0.000 claims description 11
- 239000004576 sand Substances 0.000 claims description 10
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 9
- 239000004568 cement Substances 0.000 claims description 9
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 9
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N n-hexyl alcohol Natural products CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 8
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- ZEMPKEQAKRGZGQ-AAKVHIHISA-N 2,3-bis[[(z)-12-hydroxyoctadec-9-enoyl]oxy]propyl (z)-12-hydroxyoctadec-9-enoate Chemical compound CCCCCCC(O)C\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CC(O)CCCCCC)COC(=O)CCCCCCC\C=C/CC(O)CCCCCC ZEMPKEQAKRGZGQ-AAKVHIHISA-N 0.000 claims description 5
- 230000007547 defect Effects 0.000 claims description 4
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 4
- 239000004925 Acrylic resin Substances 0.000 claims description 3
- 229920000178 Acrylic resin Polymers 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 8
- 230000000977 initiatory effect Effects 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 239000000853 adhesive Substances 0.000 abstract description 2
- 238000013035 low temperature curing Methods 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract 2
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- 125000001261 isocyanato group Chemical group *N=C=O 0.000 description 18
- 239000002002 slurry Substances 0.000 description 13
- 230000000694 effects Effects 0.000 description 12
- 239000000178 monomer Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 8
- 229920002554 vinyl polymer Polymers 0.000 description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 239000012948 isocyanate Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
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- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000013256 coordination polymer Substances 0.000 description 3
- 230000002950 deficient Effects 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 235000004443 Ricinus communis Nutrition 0.000 description 2
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- 150000002148 esters Chemical class 0.000 description 2
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- 238000005187 foaming Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000001165 hydrophobic group Chemical group 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 230000000269 nucleophilic effect Effects 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 229920005906 polyester polyol Polymers 0.000 description 2
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- 239000002994 raw material Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- 208000005156 Dehydration Diseases 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
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- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 229960001777 castor oil Drugs 0.000 description 1
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- 230000015556 catabolic process Effects 0.000 description 1
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- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 239000011440 grout Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
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- 238000001764 infiltration Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000002513 isocyanates Chemical group 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 150000007518 monoprotic acids Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 210000002445 nipple Anatomy 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
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- 229920000728 polyester Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
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Landscapes
- Macromonomer-Based Addition Polymer (AREA)
- Working Measures On Existing Buildindgs (AREA)
Abstract
The present invention relates to an epoxy/polyurethane underwater patching material of an interpenetrating polymer network, which at least comprises the following components (by weight): 90 to 110 portions of acrylic acid epoxy resin, 15 to 30 portions of polyurethane prepolymer, 30 to 60 portions of diluting agent, 0.5 to 1.0 portion of initiating agent and 0.1 to 0.2 portion of accelerating agent. The underwater patching material of an interpenetrating polymer network of the present invention has the advantages of favorable groutability, low viscosity of a primary test, slow increase of viscosity time delay, favorable mechanical properties, high strength, moderate toughness and low temperature curing in water. The underwater patching material is a multipurpose underwater patching material (which can be used as a grouting material and an adhesive agent). The present invention also relates to a preparation method and the application of the underwater patching material.
Description
Technical field
The present invention relates to a kind of subaqueous patching material, more particularly it is a kind of mesh subaqueous patching material of interpenetrating polymer of epoxy/polyurethane; The invention still further relates to the preparation method and the application of this subaqueous patching material.
Background technology
Concrete defect be hydraulic concrete buildings more generally, one of more common disease, concrete underwater portion particularly, because be under water for a long time, work under bad environment, in case produce the underwater concrete defective, to cause dam and canal seepage, operation constitutes directly harm to dam safety, causes a large amount of dehydrations of channel.But because operating requirement, many defective dams and channel do not allow a water emptying to repair, and this just requires to carry out underwater construction.Do large-area antiseepage and handle under deep water conditions, material and technology all are a great problems.Therefore study channel and the concrete dam subaqueous patching material has fairly obvious social benefit and economic benefit.
Subaqueous patching material is different with patching material waterborne, it can not be fully and water molten, must have certain wetting ability again.Patching material aspect under water at present generally adopts under water not that dispersion agent is mixed with the non-dispersible underwater concrete that is applicable to that underwater thin-layer is repaired; Filleting GBW water-swellable sealing rod etc. is arranged in the novel material, the research of these materials has promoted the patch work of concrete dam and channel, but the purposes of above-mentioned materials is all more single, as only can be as caking agent etc., and the mechanical property of material is relatively poor, because the kind of defective is various under water, therefore existing above-mentioned subaqueous patching material does not also satisfy requirements of one's work far away in addition.
Summary of the invention
The objective of the invention is to overcome the weak point of existing subaqueous patching material, and a kind of mesh subaqueous patching material of interpenetrating polymer of epoxy/polyurethane is provided.It is based on acrylic acid epoxy resin, utilize base polyurethane prepolymer for use as contain-the NCO group can with the characteristics of water reaction, be introduced in the slurries, this material combines the multiple premium properties that not saturated polyester, Resins, epoxy, urethane, first such as coagulate at material, it had both had intensity preferably, the toughness of appropriateness being arranged again, and can solidify in low temperature and water, is a kind of multi-usage patching material.
Another object of the present invention provides the preparation method of above-mentioned subaqueous patching material.
Another order 1 of the present invention be that this subaqueous patching material is being used for preparing the application of defect mending material under water.
The objective of the invention is to reach: mesh subaqueous patching material of interpenetrating polymer of epoxy/polyurethane by following measure, which comprises at least following component: acrylic acid epoxy resin 90-110 weight part, base polyurethane prepolymer for use as 15-30 weight part, thinner 30-60 weight part, initiator 0.5-1.0 weight part, promotor 0.1-0.2 weight part, cement 160-250 weight part, sand 160-250 weight part, described promotor is N, accelerine and/or three hexanol amine.
In above-mentioned subaqueous patching material, described thinner is the 30-40 weight part.
In technique scheme, described thinner is vinylbenzene or methyl methacrylate, and described initiator is a benzoyl peroxide.
In technique scheme, the ratio of NCO/OH is 2.5 in the described base polyurethane prepolymer for use as.
In technique scheme, the component of described subaqueous patching material is acrylic acid epoxy resin 100 weight parts, base polyurethane prepolymer for use as 25 weight parts, thinner 40 weight parts, initiator 0.5-1.0 weight part, promotor 0.1-0.2 weight part.
The method for preparing mesh subaqueous patching material of interpenetrating polymer of epoxy/polyurethane, described method is to get synthetic acrylic acid epoxy resin 90-110 weight part, synthetic base polyurethane prepolymer for use as 15-30 weight part, the 30-60 parts by weight diluent is added in the 90-110 parts by weight of acrylic Resins, epoxy, add the base polyurethane prepolymer for use as of 15-30 weight part again; After stirring, add the initiator of 0.5-1.0 weight part, the promotor of 0.1-0.2 weight part again, add cement 160-250 weight part again, sand 160-250 weight part mixes, and is mesh subaqueous patching material of interpenetrating polymer of epoxy/polyurethane.
The preparation method of above-mentioned subaqueous patching material, described thinner is vinylbenzene or methyl methacrylate, and described initiator is a benzoyl peroxide, and promotor is N, accelerine and/or three hexanol amine.
The preparation method of above-mentioned subaqueous patching material, Viscotrol C in the described synthetic base polyurethane prepolymer for use as: tolylene diisocyanate: the weight part of dibutyl phthalate is 100: 64.5: 18.3.
Above-mentioned subaqueous patching material is being used for preparing the application of defect mending material under water.
The composition principle of acrylic acid epoxy resin and preparation: acrylic acid epoxy resin is that Resins, epoxy and unsaturated monoprotic acid make (synthetic method of this acrylic acid epoxy resin is a prior art) in the addition reaction that catalyzer exists, and its general formula is:
According to top reaction formula as can be known: 1 mole Resins, epoxy needs 2 moles vinylformic acid.In order to guarantee that vinylformic acid reacts completely, it is more excessive that Resins, epoxy is wanted.Adopting Resins, epoxy and acrylic acid mol ratio is 1: 1.2, and when temperature of reaction was higher than 130 ℃, side reaction was fast, and gel can take place.When temperature was lower than 70 ℃, positive reaction took place hardly.The analysis-by-synthesis controlled temperature should be between 110-120 ℃.
The composition principle of base polyurethane prepolymer for use as and preparation (synthetic method of this base polyurethane prepolymer for use as is a prior art): in the isocyanic ester-the NCO group is very active, and its Sauerstoffatom and nitrogen-atoms are electronegativity, and the cloud density on the carbon atom is minimum, is positive polarity.The Sauerstoffatom electronegativity maximum of-NCO group is a nucleophilic center, can attract the hydrogen atom on the active hydrogen-contg compound molecule and generate hydroxyl, but the hydroxyl instability on the unsaturated carbon atom, resetting becomes carbamate.Its reaction equation is as follows:
nOCN-R-NCO+nHO-R
1-OH
～(CONH-R-NHCO-OR
1-O-)n
～
If the isocyanate group in the reaction is excessive, the mol ratio that is isocyanate group and hydroxyl is greater than 1, what then obtain is that end group is-base polyurethane prepolymer for use as of NCO, if moles such as hydroxyl and isocyanato in the reactant, generate the infinitely-great superpolymer of molecular weight in theory, but owing to impurity effect, the molecular weight of urethane is generally tens thousand of to more than 10 ten thousand.If hydroxyl is excessive, what then obtain is hydroxyl-terminated polyurethane.The present invention need prepare end group, and the principal element of decision performed polymer performance is isocyanate index NCO/OH.This ratio is too small, and gained performed polymer viscosity is big, and is active low; This ratio is excessive, and the performed polymer activity is too high, and too much with water reaction foaming, makes degradation, and is uneconomical.
The main raw material of synthesis of polyurethane performed polymer is to contain isocyanate group (polyisocyanates NCO) and the polyethers, polyester polyol and the Viscotrol C that contain reactive hydrogen.Isocyanic ester is divided into aliphatic isocyanates and aromatic isocyanate again, minimum with tolylene diisocyanate (TDI) viscosity in aromatic isocyanate, activity is the highest, and 2, the 4-TDI activity is greater than 2, the activity of 6-TDI, in containing the polyethers of reactive hydrogen, polyester polyol and Viscotrol C, the castor-oil plant main body of oil is a castor-oil plant alcohol glyceryl ester, and the nonpolar fatty acid of the long-chain in the castor oil component makes polymkeric substance have good hydrolytic resistance and bent rich property, and price is low, the source is wide, and is nontoxic.
The consumption metering of synthesis of polyurethane performed polymer: in 100 parts of synourin oils, the TDI consumption of required purity 98% can be calculated as follows: W
TDI=0.155NCO/OH ÷ 98%, synthesis of polyurethane performed polymer material fiting ratio is as shown in the table:
The proportioning of the base polyurethane prepolymer for use as raw material of synthetic different N CO/OH
The selection of subaqueous patching material reactive thinner: acrylic acid epoxy resin can with multiple vinyl monomer copolymerzation with cross-linking, by adding the viscosity that vinyl monomer can be regulated slurries, can be below viscosity drop to 10 centipoise with slurries as using vinylbenzene and methyl methacrylate.
Different vinylbenzene and methyl methacrylate content are as shown in the table to the influence of slurry viscosity:
| Reactive thinner content (%) | Vinylbenzene is the slurry viscosity (CP) of reactive thinner | Methyl methacrylate is the slurry viscosity (CP) of reactive thinner |
| 30 | 21605 | 12985 |
| 40 | 733 | 283 |
| 50 | 28 | 12 |
| 60 | 4.0 | 1.8 |
According to last table as can be seen, when the content of thinner was 50%, the viscosity of slurries was lower, when the content of thinner is 30-40%, and the modest viscosity of slurries.
The reaction mechanism of subaqueous patching material of the present invention: the acrylic acid epoxy resin curing reaction that contains vinyl monomer belongs to radical polymerization, and its reaction mechanism is: chain draws length, chainpropagation, chain termination three phases.Vinyl monomer not only can take place autohemagglutination but also can with acrylic acid epoxy resin generation copolyreaction, its reaction mechanism is: (1) chain initiation stage: the initiator benzoyl peroxide is at accelerant N, under the effect of accelerine, produce radical, through R? expression, radical acts on vinyl monomer and acrylic acid epoxy resin molecule, excite the πDian Zi cloud on two keys, generate new radical, do you use R-M? the expression acrylic acid epoxy resin, do you use R-N? expression vinyl monomer radical, this chain initiation stage in this stage; (2) the chainpropagation stage: new radical continuation and vinyl monomer and acrylic acid epoxy resin effect that initiating stage generates, excite the πDian Zi cloud on two keys, make it to be separated into two independent P electronics, radical and one of them P electronics are combined into new σ chain, generate simultaneously new radical again, rapid like this repetition repeatedly carried out, and this stage is chainpropagation.Reaction formula is as follows:
R-M+MR-M-M .......
R-M+NR-M-N .......
R-N+NR-N-N .......
R-N+MR-N-M .......
(3) termination step: in propagation process, if independent P electronic cloud collides mutually and is combined into the σ chain on two radical ends that increasing, chainpropagation has just stopped like this, and this stage is the end stopping of chain stage.Reaction formula is as follows:
R-M-(M)n-N+R-N-(N)m-MR-M-(M)n-N-M-(N)m-N-R
On the other hand in the base polyurethane prepolymer for use as-the NCO group is very active, its Sauerstoffatom and nitrogen-atoms are electronegativity, and the cloud density on the carbon atom is minimum, is positive polarity.The Sauerstoffatom electronegativity maximum of-NCO group is a nucleophilic center, can with the atomic reaction of hydrogen of acrylic acid epoxy resin, the main reaction that isocyanic ester and water take place in water, reaction formula is as follows:
2RNCO+H
2ORNHCONHR+CO
2
The bad epoxy resins of vinylformic acid that contains vinyl monomer is twined mutually with the polymkeric substance that base polyurethane prepolymer for use as generates in reaction, forms interpenetrating structure.
In water when bonding, because of by the adsorption on sticky object surface, all soak in each slit and the crack and expired water, and because the effect of London force, the interface forms the moisture film with strong adhesive power, these have seriously hindered caking agent by the infiltration of maxxaedium and diffusion, can't obtain higher bonding strength so only contain hydrophobic group.When contain a certain amount of and-OH reactive higher-during the NCO group, in impregnation process, moisture film speed goes to pot, the water in the slit also identifies oneself with in the curing reaction of caking agent, soaks into and spreads smooth.With the acrylic acid epoxy is matrix, introduce the polymer-modified elastomerics of a certain amount of containing-NCO group, in resin based on the hydrophobic group, contain with-OH reactive behavior more-the NCO group, it destroys the interface moisture film in bonding, promote the interface to soak into and obtain bonding strength in the water.
Base polyurethane prepolymer for use as optimum N CO/OH determines: under water in the slurries of patching material, if the NCO/OH ratio of performed polymer is excessive, activity is too high, free toluene diisocyanate (TDI) is too much, then easily and have in the molecule bonding active group-the OH reaction, makes resin gel or reduce bonding activity, and it is too much to meet the water foaming, form hole at bonding plane, these all make bonding strength descend; If ratio is too small, the performed polymer activity is too low, can not destroy effectively by the moisture film on the sticking face, and bonding strength is descended.Therefore, the NCO/OH ratio that subaqueous patching material is just had a best.The ratio that the experiment proved that NCO/OH is 2.5 o'clock, and water bonding strength maximum is arranged, with analyze consistent.
Mesh subaqueous patching material of interpenetrating polymer of the present invention, it adopts two kinds of polymkeric substance to run through mutually in polymerization process and forms the network interlocking structure, thereby polymkeric substance had be better than the performance of any single component, this project is based on acrylic acid epoxy resin, utilize base polyurethane prepolymer for use as contain-the NCO group can with the characteristics of water reaction, be introduced in the slurries.Both had good concrete castability, i.e. preliminary examination viscosity is low, viscosity along the time increase slowly, have the good mechanical performance again; Have intensity preferably, the toughness of appropriateness is arranged again, and can be in water and low-temperature curing, be a kind of multi-usage subaqueous patching material of (can be used as injection material and caking agent).
Embodiment
Embodiment 1
Mesh subaqueous patching material of interpenetrating polymer of epoxy/polyurethane, it forms (consumption is a weight part) by following component: acrylic acid epoxy resin 100, base polyurethane prepolymer for use as (NCO/OH is 2.5) 25, vinylbenzene (thinner) 50, benzoyl peroxide (initiator) 0.5-1.0, N, accelerine (promotor) 0.1-0.2.
The preparation method of above-mentioned mesh subaqueous patching material of interpenetrating polymer of epoxy/polyurethane, it comprises the steps:
Base polyurethane prepolymer for use as synthetic, acrylic acid epoxy resin synthetic; The synthetic method of described base polyurethane prepolymer for use as is: the Viscotrol C of 90-100 weight part, the dibutyl phthalate of 15-25 weight part are poured in the reactant, stir, the tolylene diisocyanate that adds the 35-95 weight part again adds while stirring, is cooled to 20-30 ℃ again when allowing it be warming up to 60 ℃ naturally, slowly heating again, and constantly stir, control reaction temperature is at 70-80 ℃, behind the 1.5h, can stop heating, discharging;
The synthetic method of described acrylic acid epoxy resin is: with 250 weight part Resins, epoxy, when being heated to 80-90 ℃, slowly add 90 parts by weight of acrylic, catalyzer is that benzyl trimethyl ammonium chloride, stopper are the cinnamic mixture of Resorcinol and 85 weight parts, control reaction temperature is at 110-120 ℃, about 1h adds, and continues reaction 1h, and the question response thing is cooled to 50 ℃, discharging promptly obtains containing 20% cinnamic acrylic acid epoxy resin solution;
Get aforesaid method synthetic acrylic acid epoxy resin 100 weight parts, base polyurethane prepolymer for use as 25 weight parts, 50 parts by weight diluent are added in the 100 parts by weight of acrylic Resins, epoxy, add the base polyurethane prepolymer for use as of 25 weight parts again; After stirring, add the initiator of 0.5-1.0 weight part, the promotor of 0.1-0.2 weight part again; Be mesh subaqueous patching material of interpenetrating polymer of epoxy/polyurethane.
Embodiment 2
Mesh subaqueous patching material of interpenetrating polymer of epoxy/polyurethane, it forms (consumption is a weight part) by following component: acrylic acid epoxy resin 100, base polyurethane prepolymer for use as (NCO/OH is 2.5) 25, methacrylic methyl esters (thinner) 50, Benzoyl Peroxide (initiator) 0.5-1.0, N, accelerine (promotor) 0.05-0.10, three hexanol amine, 0.1 weight part.
The preparation method is with embodiment 1.
It is as follows that embodiment 1,2 subaqueous patching materials are carried out physical and mechanical property (length of time: 28 days) test:
| Embodiment | Initial viscosity (CP) | Gelation time (Min) | Ultimate compression strength (MPa) | Bonding strength (MPa) | Tensile strength (MPa) | Breaking tenacity (MPa) | Elongation (%) |
| 1 | 150 | Several-tens | 76.8 | 1.40 | 12 | 26.8 | 11 |
| 2 | 96 | Several-tens | 72.3 | 1.33 | 10.5 | 25.5 | 10 |
Below for investigating the experiment of mesh subaqueous patching material of interpenetrating polymer of epoxy/polyurethane concrete castability of the present invention: test is with 15 * 15 * 15cm
3The concrete test block splitting open after amalgamation again, respectively paste a grout nipple and exhaust nozzle along diagonal lines two, use the epoxy glue joint seal, the concrete test block of sealing seam is filled water and put into water be in the milk, treat that slurries eject back screen slurry to water, the test specimen after the filling still is placed on to soak up to test in the water and takes out.The 28 day length of time, bonding tensile splitting strength embodiment 1 was 1.21Mpa, and embodiment 2 is 1.10Mpa.
Embodiment 3
Mesh subaqueous patching material of interpenetrating polymer of epoxy/polyurethane, it forms (consumption is a weight part) by following component: acrylic acid epoxy resin 100, base polyurethane prepolymer for use as (NCO/OH is 2.5) 25, vinylbenzene (thinner) 40, Benzoyl Peroxide (initiator) 0.5-1.0, N, accelerine (promotor) 0.1-0.2, cement 200, sand 200.
The preparation method is: after pressing embodiment 1 preparation, add cement 200 weight parts again, sand 200 weight parts mix, sand is crossed the 0.63mm sieve, need to prove that the ratio of cement and sand can suitably increase and decrease in actual applications, the use to subaqueous patching material of the present invention there is no bigger influence generally speaking.
Embodiment 4
Mesh subaqueous patching material of interpenetrating polymer of epoxy/polyurethane, it forms (consumption is a weight part) by following component: acrylic acid epoxy resin 100, base polyurethane prepolymer for use as (NCO/OH is 2.5) 25, methacrylic methyl esters (thinner) 40, benzoyl peroxide (initiator) 0.5-1.0, N, accelerine (promotor) 0.05-0.10, three hexanol amine (promotor) 0.1, cement 200, sand 200.
The preparation method is with embodiment 3.
Subaqueous patching material is when caking agent is constructed under water under water, because the influence of water, diluting effect that must anti-sealing could solidify and have certain mechanical property well in water.Therefore material prescription requires slurry viscosity moderate (viscosity is too low, is unfavorable for facade and thin layer repairing under water, and viscosity is too big, and construction is inconvenient again) under the prerequisite of considering the induration mechanical property.
Blanks and moulding and conserving in the water of embodiment 3,4, find in the test that the subaqueous patching material added cement and sand does not disperse in water, self-compacting, from levelling, and in water, reach certain intensity in the short period of time, its folding strength and tensile strength are higher, illustrate that subaqueous patching material of the present invention is crisp firmly and not, is applicable to quick repairing.
The physical and mechanical property that embodiment 3,4 subaqueous patching materials carry out is tested:
| The length of time | Ultimate compression strength (MPa) | Folding strength (MPa) | Bonding strength (MPa) | Tensile strength (MPa) | ||||
| Embodiment 3 | Embodiment 4 | Embodiment 3 | Embodiment 4 | Embodiment 3 | Embodiment 4 | Embodiment 3 | Embodiment 4 | |
| ?6h | ?18.7 | ?15.6 | ?8.62 | ?8.50 | ?0.30 | ?0.21 | ?8.0 | ?7.50 |
| ?12h | ?20.6 | ?18.8 | ?9.60 | ?9.10 | ?0.52 | ?0.42 | ?8.75 | ?7.80 |
| ?24h | ?30.2 | ?28.8 | ?9.90 | ?9.60 | ?0.89 | ?0.79 | ?8.80 | ?8.20 |
| ?48h | ?40.5 | ?38.5 | ?11.5 | ?11.2 | ?1.12 | ?1.02 | ?8.90 | ?8.60 |
Embodiment 5
Mesh subaqueous patching material of interpenetrating polymer of epoxy/polyurethane, it comprises following component: acrylic acid epoxy resin 90 weight parts, base polyurethane prepolymer for use as 15 weight parts, vinylbenzene 30 weight parts, benzoyl peroxide 0.5 weight part, N, accelerine 0.05 weight part, three hexanol amine, 0.06 weight part.
The preparation method is with embodiment 1.
Embodiment 6
Mesh subaqueous patching material of interpenetrating polymer of epoxy/polyurethane, it comprises following component: acrylic acid epoxy resin 110 weight parts, base polyurethane prepolymer for use as 30 weight parts, vinylbenzene 60 weight parts, benzoyl peroxide 1.0 weight parts, N, accelerine 0.10 weight part, three hexanol amine, 0.12 weight part.
The preparation method is with embodiment 1.
Embodiment 7
Mesh subaqueous patching material of interpenetrating polymer of epoxy/polyurethane is characterized in which comprises at least following component: acrylic acid epoxy resin 95 weight parts, base polyurethane prepolymer for use as 25 weight parts, thinner 45 weight parts, initiator 0.8 weight part, promotor 0.16.
The preparation method is with embodiment 1.
Embodiment 8
Mesh subaqueous patching material of interpenetrating polymer of epoxy/polyurethane, it is characterized in which comprises at least following component: acrylic acid epoxy resin 105 weight parts, base polyurethane prepolymer for use as 20 weight parts, thinner 35 weight parts, initiator 0.75 weight part, promotor 0.165 weight part.
The preparation method is with embodiment 1.
Need to prove: to those of ordinary skill in the art, can also make some changes or distortion to the present invention under the prerequisite that does not change the principle of the invention, this belongs to protection scope of the present invention equally.
Claims (9)
1, mesh subaqueous patching material of interpenetrating polymer of epoxy/polyurethane, it is characterized in which comprises at least following component: acrylic acid epoxy resin 90-110 weight part, base polyurethane prepolymer for use as 15-30 weight part, thinner 30-60 weight part, initiator 0.5-1.0 weight part, promotor 0.1-0.2 weight part, cement 160-250 weight part, sand 160-250 weight part, described promotor is N, accelerine and/or three hexanol amine.
2, mesh subaqueous patching material of interpenetrating polymer of epoxy/polyurethane according to claim 1 is characterized in that described thinner is the 30-40 weight part.
3, mesh subaqueous patching material of interpenetrating polymer of epoxy/polyurethane according to claim 1 is characterized in that described thinner is vinylbenzene or methyl methacrylate, and described initiator is a benzoyl peroxide.
4, mesh subaqueous patching material of interpenetrating polymer of epoxy/polyurethane according to claim 1, the ratio that it is characterized in that NCO/OH in the described base polyurethane prepolymer for use as is 2.5.
5, mesh subaqueous patching material of interpenetrating polymer of epoxy/polyurethane according to claim 1 is characterized in that described component is acrylic acid epoxy resin 100 weight parts, base polyurethane prepolymer for use as 25 weight parts, thinner 40 weight parts, initiator 0.5-1.0 weight part, promotor 0.1-0.2 weight part.
6, the method for preparing the described mesh subaqueous patching material of interpenetrating polymer of epoxy/polyurethane of claim 1, it is characterized in that described method is to get synthetic acrylic acid epoxy resin 90-110 weight part, synthetic base polyurethane prepolymer for use as 15-30 weight part, the 30-60 parts by weight diluent is added in the 90-110 parts by weight of acrylic Resins, epoxy, add the base polyurethane prepolymer for use as of 15-30 weight part again; After stirring, add the initiator of 0.5-1.0 weight part, the promotor of 0.1-0.2 weight part again, add cement 160-250 weight part again, sand 160-250 weight part mixes, and is mesh subaqueous patching material of interpenetrating polymer of epoxy/polyurethane.
7, the preparation method of mesh subaqueous patching material of interpenetrating polymer of epoxy/polyurethane according to claim 6, it is characterized in that described thinner is vinylbenzene or methyl methacrylate, described initiator is a benzoyl peroxide, and promotor is N, accelerine and/or three hexanol amine.
8, the preparation method of mesh subaqueous patching material of interpenetrating polymer of epoxy/polyurethane according to claim 6 is characterized in that Viscotrol C in the described synthetic base polyurethane prepolymer for use as: tolylene diisocyanate: the weight part of dibutyl phthalate is 100: 64.5: 18.3.
9, the described subaqueous patching material of arbitrary claim is being used for preparing the application of defect mending material under water among the aforesaid right requirement 1-5.
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| CN112408879B (en) * | 2020-11-18 | 2022-07-12 | 临沂大学 | High-strength fast-curing epoxy/styrene-acrylic resin composite grouting repair material and preparation method and application thereof |
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