CN105198300A - Modified polyurethane/epoxy resin composite grouting cement mortar and preparation method thereof - Google Patents
Modified polyurethane/epoxy resin composite grouting cement mortar and preparation method thereof Download PDFInfo
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- CN105198300A CN105198300A CN201510686417.2A CN201510686417A CN105198300A CN 105198300 A CN105198300 A CN 105198300A CN 201510686417 A CN201510686417 A CN 201510686417A CN 105198300 A CN105198300 A CN 105198300A
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Abstract
The invention relates to modified polyurethane/epoxy resin composite grouting cement mortar and a preparation method thereof, belonging to the field of building materials. The mortar is prepared from the following components in parts by weight: 80 to 100 parts of cement, 120 to 180 parts of fine sand of 50 to 200 meshes, 20 to 50 parts of water, 4 to 7 parts of sodium silicate, 2 to 3 parts of aluminum sulfate, 1 to 2 parts of calcium chloride, 1 to 2 parts of sodium hydroxide, 10 to 15 parts of polyurethane modified epoxy resin toughening emulsion containing modified wood fiber, 1.5 to 6 parts of early strength agent and 0.9 to 2.4 parts of water reducing agent. On the basis of a modified polyurethane/epoxy resin composite material, the modified wood fiber is further compounded to facilitate the crack resistance of the grouting mortar, improve the toughness and reduce the later maintenance cost of engineering.
Description
Technical field
The present invention relates to a kind of modified polyurethane/epoxy resin compound grouting sand-cement slurry and preparation method thereof, belong to building material field.
Background technology
Ordinary mortar because of tensile pressure ratio low, greatly dry-shrinkage deformed, impermeability, splitting resistance, corrosion-resistant, density is large, and its use range is very restricted.Along with industrial expansion, the performance of mortar to be improved further, the performance of consolidating material will be improved, therefore occur polymer mortar.Utilizing polymkeric substance to carry out modification to sand-cement slurry makes it when keeping cement original inorganic materials ultimate compression strength, folding strength, ageing-resistant advantage, add the feature that organic materials cohesive force is large, deformability good, stopping property is strong, thus the cohesive force of sand-cement slurry, frost resistance and impervious power are all enhanced.The Grouting Cement mortar that current Application comparison is many mainly contains two kinds: one is epoxy resin grouting sand-cement slurry, another is urethane Grouting Cement mortar, but adopt single its toughness of epoxy resin grouting sand-cement slurry poor, adopt single its intensity of urethane Grouting Cement mortar inadequate again, therefore, how to combine both advantages, determine that a kind of high performance Grouting Cement mortar is construction work problem in the urgent need to address.Epoxy resin has many advantages, as the chemical stability of excellence, erosion resistance, electrical apparatus insulation and shrinking percentage low etc.But due to cross-linking density after single epoxy resin cure high, in tridimensional network, there is internal stress large, matter is crisp, poor impact resistance, and easily the shortcoming such as cracking, is difficult to meet the toughness reinforcing engineering requirement of concrete, makes it apply and be subject to certain restrictions.For a long time, carry out toughening modifying to epoxy resin is an important research contents always.Urethane is the polymer of a class excellent property, has high impact strength and excellent resistance to low temperature, both can be made to have complementary advantages with polyurethane modified epoxy resin.Utilize epoxy resin latex in polyurethane-modified process, the structure of microcosmic interpenetrating(polymer)networks can be formed, thus make concrete material show good toughness, intensity, fatigue resistance and isotropy, again innovation wood fiber is added again, form composite toughening material, the effect of bi-material coordination plasticizing can be played better, bring great improvement to concrete performance.
Xylon first after through silane coupling agent and maleic anhydride graft terpolymer modified, its mechanical property is more excellent, and ageing-resistant and anti-hydrolytic performance significantly improves, and is a kind of desirable concrete toughened fiber material.Therefore, on the basis of modified polyurethane/epoxy resin composite material, further composite modified xylon, advantageously in the splitting resistance of grouting mortar, increases toughness, reduces engineering later maintenance expense.
Summary of the invention
The object of the invention is to for the deficiencies in the prior art, a kind of modified polyurethane/epoxy resin compound grouting sand-cement slurry and preparation method thereof is provided, on the basis of modified polyurethane/epoxy resin composite material, further composite modified xylon, advantageously in the splitting resistance of grouting mortar, increase toughness, reduce engineering later maintenance expense.
In order to reach the object of the invention, adopt following technical scheme:
1. prepare innovation wood fiber
1) add in high-speed mixer by the wood powder of drying, stir at 80-90 DEG C, and add the aluminate coupling agent of wood powder weight 2% at twice, twice joining day interval 3-4min, stirs 5-6min again after adding, obtains the wood powder after activation;
2) get the wood powder after the activated process of 200 weight part, be added in 60-80 weight part coupling agent aqueous solution, stir 0.4h; Then be heated to 60-62 DEG C, stir 5-8h; Filter, the wood powder after filtration adds in whizzer, and rotating speed is 500r/min, takes out after centrifugal 15min;
3) the wood powder vacuum-drying at 50-55 DEG C after taking out, after 24 hours, is cooled to 20-28 DEG C; The maleic anhydride graft copolymer of wood powder and 100-150 weight part is loaded in high-speed mixer, high-speed mixer rotating speed is 300r/min, after rotating mixing 1-2h, be heated to 80-100 DEG C, mix 10-15min under 400-450r/min rotating speed after, blowing when being then cooled to 45 DEG C, obtains just batch mixing;
4) loaded in twin screw extruder by first batch mixing, the temperature in twin screw extruder is 160-170 DEG C, rotating speed is 50-60r/min, extrudes after mixing 0.5h;
5) after obtaining extruded stock, carry out pulverization process to extruded stock material, obtaining granularity is 50-70 object innovation wood fiber.
Step 2) described in coupling agent be silane coupling agent, preferred U.S. union carbide corporation's trade mark is the silane coupling agent of A-151 or A-171.
Described wood powder particle diameter is 50-70 order.
2. preparation is containing innovation wood fiber and the toughness reinforcing emulsion of polyurethane modified epoxy resin
1) 100-120 weight of polyester polyvalent alcohol is got, at 90-110 DEG C of heating 30min;
2) after being cooled to 45 DEG C, 20-25 weight part diphenylmethanediisocyanate being added, then is warming up to 70 DEG C, react after 3 hours, be cooled to room temperature;
3) in step 2) solution in add 10-12 weight part TriMethylolPropane(TMP) and 100-150 weight part 2,3-butanediol again, and vibration stirs to obtain mixed solution; Then by mixed solution and 150-200 parts by weight epoxy resin, 10-15 weight part triphenylphosphine is added in 80-100 part by weight of n-butanol together;
4) while stirring, 90 DEG C are warming up to, temperature-rise period used time 0.6h; Then be cooled to 75 DEG C, continue to stir 1h; Be cooled to 25-30 DEG C and obtain emulsion, with the pH regulator to 8 of ammoniacal liquor by emulsion;
5) part by weight modified for 30-50 xylon is joined in the emulsion of step 4) at 25-30 DEG C, and after continuing to stir 1h at 25 DEG C, obtain the toughness reinforcing emulsion of polyurethane modified epoxy resin containing innovation wood fiber.
Described ammoniacal liquor is the commercially available aqueous solution containing ammonia 25-28%.
Modified polyurethane of the present invention/epoxy resin compound grouting sand-cement slurry, by weight, cement 80 ~ 100 parts, 50 ~ 200 object fine sand 120 ~ 180 parts, 20 ~ 50 parts, water, water glass 4-7 part, Tai-Ace S 150 2-3 part, calcium chloride 1-2 part, sodium hydroxide 1-2 part, the toughness reinforcing emulsion 10-15 part of polyurethane modified epoxy resin containing innovation wood fiber, hardening accelerator 1.5 ~ 6 parts, water reducer 0.9 ~ 2.4 part is comprised.
In described toughness reinforcing emulsion, the mass content of innovation wood fiber is 15 ~ 25%;
Described hardening accelerator is one or more in villaumite, vitriol, nitric acid, nitrite, trolamine, calcium formiate, acetic acid, acetate;
Described water reducer is one or more of naphthalenesulfonate formaldehyde condensation compound and sulfonated melamine compound condenses;
Cement used is 42.5 grades of ordinary Portland cements.
A preparation method for modified polyurethane/epoxy resin compound grouting sand-cement slurry, comprises the following steps:
1) cement and fine sand are mixed formation dry mash, then adding water stirs;
2) hardening accelerator and water reducer are added successively in the mixture that step (1) formed, stir, the time is respectively 5 ~ 8 minutes;
3) add in the obtained mixture of step (2) containing the toughness reinforcing emulsion of polyurethane modified epoxy resin of innovation wood fiber, water glass, Tai-Ace S 150, calcium chloride, sodium hydroxide simultaneously, rapid stirring is even, is then pumped into by pressure pump and specifies engineered locations.
The Grouting Cement mortar that current Application comparison is many mainly contains two kinds: one is epoxy resin grouting sand-cement slurry, another is urethane Grouting Cement mortar, but adopt single its toughness of epoxy resin grouting sand-cement slurry poor, adopt single its intensity of urethane Grouting Cement mortar inadequate again, and the invention solves this problem.
beneficial effect of the present invention is:
1) the present invention is on the basis of modified polyurethane/epoxy resin composite material, further composite modified xylon, obtain a kind of concrete composite toughing agent, and this toughner can make cement mortar fast setting when slip casting, advantageously in the splitting resistance of grouting mortar, increase toughness, reduce engineering later maintenance expense;
2) after adopting mortar of the present invention to be in the milk, there is very high intensity, can 40MPa be reached, there is good toughness and splitting resistance.
Embodiment
The present invention's the following example further illustrates the present invention, but protection scope of the present invention is not limited to the following example.
embodiment 1
1. prepare innovation wood fiber
1) add in high-speed mixer by the wood powder of drying, stir at 80 DEG C, and add the aluminate coupling agent of wood powder weight 2% at twice, twice joining day interval 3min, stirs 5min again after adding, obtains the wood powder after activation;
2) get the wood powder after the activated process of 200 weight part, be added in 60 weight part coupling agent aqueous solutions and (0.5 weight part coupling agent joined in 80 weight parts waters, is stirred to it and dissolves completely), stir 0.4h; Then be heated to 61 DEG C, stir 6h; Filter, the wood powder after filtration adds in whizzer, and rotating speed is 500r/min, takes out after centrifugal 15min;
3) the wood powder vacuum-drying at 53 DEG C after taking out, after 24 hours, is cooled to 24 DEG C; Wood powder and 100 parts by weight maleic anhydride graft copolymers are loaded in high-speed mixer, high-speed mixer rotating speed is 300r/min, after rotating mixing 1h, be heated to 90 DEG C, mix 12min under 400r/min rotating speed after, blowing when being then cooled to 45 DEG C, obtains just batch mixing;
4) loaded in twin screw extruder by first batch mixing, the temperature in twin screw extruder is 165 DEG C, rotating speed is 55r/min, extrudes after mixing 0.5h;
5) after obtaining extruded stock, carry out pulverization process to extruded stock material, obtaining granularity is 60 object innovation wood fibers.
2. preparation is containing innovation wood fiber and the toughness reinforcing emulsion of polyurethane modified epoxy resin
1) 110 weight of polyester polyvalent alcohols are got, at 100 DEG C of heating 30min;
2) after being cooled to 45 DEG C, 23 weight part diphenylmethanediisocyanates being added, then is warming up to 70 DEG C, react after 3 hours, be cooled to room temperature;
3) in step 2) solution in add 11 weight part TriMethylolPropane(TMP)s and 100 weight part 2,3-butanediols again, and vibration stirs to obtain mixed solution; Then by mixed solution and 170 parts by weight epoxy resin, 13 weight part triphenylphosphines are added in 90 part by weight of n-butanol together;
4) while stirring, 90 DEG C are warming up to, temperature-rise period used time 0.6h; Then be cooled to 75 DEG C, continue to stir 1h; Be cooled to 25-30 DEG C and obtain emulsion, with the pH regulator to 8 of ammoniacal liquor by emulsion;
5) 40 part by weight modified xylons are joined in the emulsion of step 4) at 27 DEG C, and after continuing to stir 1h at 25 DEG C, obtain the toughness reinforcing emulsion of polyurethane modified epoxy resin containing innovation wood fiber.
3. the preparation of modified polyurethane/epoxy resin compound grouting sand-cement slurry
1) preparation is stand-by containing the toughness reinforcing emulsion of polyurethane modified epoxy resin of innovation wood fiber according to the method described above;
2) by cement by weight 80 parts and fine sand 160 parts mix formation dry mash, then add 35 weight parts waters and stir;
3) hardening accelerator 3 parts and water reducer 2 parts added successively in the mixture that step (2) formed and stir, the time is respectively 7 minutes;
4) be added in the obtained mixture of step (3) containing the toughness reinforcing emulsion of polyurethane modified epoxy resin 18 parts of innovation wood fiber, water glass 5 parts, 2 parts, Tai-Ace S 150,1.5 parts, calcium chloride, 1.5 parts, sodium hydroxide simultaneously, rapid stirring is even, is then pumped into appointment engineered locations by pressure pump.
The present embodiment records the ultimate compression strength of 28 days urethane sand, folding strength, cohesive strength and water-intake rate and shrinking percentage is 58.26MPa, 19.4MPa, 4.3MPa, 0.23% and 0.27% respectively.
embodiment 2
1. prepare innovation wood fiber
1) add in high-speed mixer by the wood powder of drying, stir at 90 DEG C, and add the aluminate coupling agent of wood powder weight 2% at twice, twice joining day interval 4min, stirs 6min again after adding, obtains the wood powder after activation;
2) get the wood powder after the activated process of 200 weight part, be added in the coupling agent aqueous solution of 80 weight parts and (1 weight part coupling agent joined in 100 weight parts waters, is stirred to it and dissolves completely), stir 0.4h; Then be heated to 60 DEG C, stir 8h; Filter, the wood powder after filtration adds in whizzer, and rotating speed is 500r/min, takes out after centrifugal 15min;
3) the wood powder vacuum-drying at 55 DEG C after taking out, after 24 hours, is cooled to 28 DEG C; Wood powder and 150 parts by weight maleic anhydride graft copolymers are loaded in high-speed mixer, high-speed mixer rotating speed is 300r/min, after rotating mixing 2h, be heated to 80 DEG C, mix 10min under 450r/min rotating speed after, blowing when being then cooled to 45 DEG C, obtains just batch mixing;
4) loaded in twin screw extruder by first batch mixing, the temperature in twin screw extruder is 170 DEG C, rotating speed is 50r/min, extrudes after mixing 0.5h;
5) after obtaining extruded stock, carry out pulverization process to extruded stock material, obtaining granularity is 50-70 object innovation wood fiber.
2. preparation is containing innovation wood fiber and the toughness reinforcing emulsion of polyurethane modified epoxy resin
1) 100 weight of polyester polyvalent alcohols are got, at 110 DEG C of heating 30min;
2) after being cooled to 45 DEG C, 25 weight part diphenylmethanediisocyanates being added, then is warming up to 70 DEG C, react after 3 hours, be cooled to room temperature;
3) in step 2) solution in add 10 weight part TriMethylolPropane(TMP)s and 150 weight part 2,3-butanediols again, and vibration stirs to obtain mixed solution; Then by mixed solution and 150 parts by weight epoxy resin, 15 weight part triphenylphosphines are added in 100 part by weight of n-butanol together;
4) while stirring, 90 DEG C are warming up to, temperature-rise period used time 0.6h; Then be cooled to 75 DEG C, continue to stir 1h; Be cooled to 25 DEG C and obtain emulsion, with the pH regulator to 8 of ammoniacal liquor by emulsion;
5) 30 part by weight modified xylons are joined in the emulsion of step 4) at 30 DEG C, and after continuing to stir 1h at 25 DEG C, obtain the toughness reinforcing emulsion of polyurethane modified epoxy resin containing innovation wood fiber.
3. the preparation of modified polyurethane/epoxy resin compound grouting sand-cement slurry
1) preparation is stand-by containing the toughness reinforcing emulsion of polyurethane modified epoxy resin of innovation wood fiber according to the method described above;
2) by cement by weight 90 parts and fine sand 160 parts mix formation dry mash, then add 50 weight parts waters and stir;
3) hardening accelerator 3.8 parts and water reducer 2.8 parts be added to successively in the mixture that step (2) formed and stir, the time is respectively 6 minutes;
4) add in the obtained mixture of step (3) containing the toughness reinforcing emulsion of polyurethane modified epoxy resin 25 parts of innovation wood fiber, water glass 3.8 parts, 2 parts, Tai-Ace S 150,1.6 parts, calcium chloride, 1.8 parts, sodium hydroxide simultaneously, rapid stirring is even, is then pumped into appointment engineered locations by pressure pump.
The present embodiment records the ultimate compression strength of 28 days urethane sand, folding strength, cohesive strength and water-intake rate and shrinking percentage is 59.45MPa, 19.8MPa, 4.7MPa, 0.25% and 0.28% respectively.
The foregoing is only preferred embodiment of the present invention, all equalizations done according to the present patent application the scope of the claims change and modify, and all should belong to covering scope of the present invention.
Claims (6)
1. modified polyurethane/epoxy resin compound grouting sand-cement slurry, it is characterized in that: by weight, component comprises: cement 80 ~ 100 parts, 50 ~ 200 object fine sand 120 ~ 180 parts, 20 ~ 50 parts, water, water glass 4-7 part, Tai-Ace S 150 2-3 part, calcium chloride 1-2 part, sodium hydroxide 1-2 part, the toughness reinforcing emulsion 10-15 part of polyurethane modified epoxy resin containing innovation wood fiber, hardening accelerator 1.5 ~ 6 parts, water reducer 0.9 ~ 2.4 part;
In described toughness reinforcing emulsion, the mass content of innovation wood fiber is 15 ~ 25%.
2. modified polyurethane according to claim 1/epoxy resin compound grouting sand-cement slurry, is characterized in that: the preparation method of described innovation wood fiber, comprises the following steps:
1) add in high-speed mixer by the wood powder of drying, stir at 80-90 DEG C, and add the aluminate coupling agent of wood powder weight 2% at twice, twice joining day interval 3-4min, stirs 5-6min again after adding, obtains the wood powder after activation;
2) get the wood powder after the activated process of 200 weight part, be added in 60-80 weight part coupling agent aqueous solution, stir 0.4h; Then be heated to 60-62 DEG C, stir 5-8h; Filter, the wood powder after filtration adds in whizzer, and rotating speed is 500r/min, takes out after centrifugal 15min;
3) the wood powder vacuum-drying at 50-55 DEG C after taking out, after 24 hours, is cooled to 20-28 DEG C; Wood powder and 100-150 parts by weight maleic anhydride graft copolymer are loaded in high-speed mixer, high-speed mixer rotating speed is 300r/min, after rotating mixing 1-2h, be heated to 80-100 DEG C, mix 10-15min under 400-450r/min rotating speed after, blowing when being then cooled to 45 DEG C, obtains just batch mixing;
4) loaded in twin screw extruder by first batch mixing, the temperature in twin screw extruder is 160-170 DEG C, rotating speed is 50-60r/min, extrudes after mixing 0.5h;
5) after obtaining extruded stock, carry out pulverization process to extruded stock material, obtaining granularity is 50-70 object innovation wood fiber.
3. modified polyurethane according to claim 1/epoxy resin compound grouting sand-cement slurry, is characterized in that: the preparation method of the described toughness reinforcing emulsion of polyurethane modified epoxy resin containing innovation wood fiber, comprises the following steps:
1) 100-120 weight of polyester polyvalent alcohol is got, at 90-110 DEG C of heating 30min;
2) after being cooled to 45 DEG C, 20-25 weight part diphenylmethanediisocyanate being added, then is warming up to 70 DEG C, react after 3 hours, be cooled to room temperature;
3) in step 2) solution in add 10-12 weight part TriMethylolPropane(TMP) and 100-150 weight part 2,3-butanediol again, and vibration stirs to obtain mixed solution; Then by mixed solution and 150-200 parts by weight epoxy resin, 10-15 weight part triphenylphosphine is added in 80-100 part by weight of n-butanol together;
4) while stirring, 90 DEG C are warming up to, temperature-rise period used time 0.6h; Then be cooled to 75 DEG C, continue to stir 1h; Be cooled to 25-30 DEG C and obtain emulsion, with the pH regulator to 8 of ammoniacal liquor by emulsion;
5) part by weight modified for 30-50 xylon is joined in the emulsion of step 4) at 25-30 DEG C, and after continuing to stir 1h at 25 DEG C, obtain the toughness reinforcing emulsion of polyurethane modified epoxy resin containing innovation wood fiber.
4. modified polyurethane according to claim 1/epoxy resin compound grouting sand-cement slurry, is characterized in that: described hardening accelerator is one or more in villaumite, vitriol, nitric acid, nitrite, trolamine, calcium formiate, acetic acid, acetate.
5. modified polyurethane according to claim 1/epoxy resin compound grouting sand-cement slurry, is characterized in that: described water reducer be naphthalenesulfonate formaldehyde condensation compound, sulfonated melamine compound condenses one or more.
6. prepare a method for modified polyurethane as claimed in claim 1/epoxy resin compound grouting sand-cement slurry, it is characterized in that: comprise the following steps:
1) cement and fine sand are mixed formation dry mash, then adding water stirs;
2) hardening accelerator and water reducer are added successively in the mixture that step (1) formed, stir, the time is respectively 5 ~ 8 minutes;
3) add in the obtained mixture of step (2) containing the toughness reinforcing emulsion of polyurethane modified epoxy resin of innovation wood fiber, water glass, Tai-Ace S 150, calcium chloride, sodium hydroxide simultaneously, rapid stirring is even, is then pumped into by pressure pump and specifies engineered locations.
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| CN107200515A (en) * | 2017-05-31 | 2017-09-26 | 福建江夏学院 | A kind of high tenacity cement mortar and preparation method thereof |
| CN107434428A (en) * | 2017-08-22 | 2017-12-05 | 绍兴职业技术学院 | A kind of preparation method that the permeable mortar of the high-elastic mould of pouring type self-compaction is produced using building waste |
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| CN111499336A (en) * | 2020-04-30 | 2020-08-07 | 山东大学 | Cuttable material for reinforcing tunnel portal |
| CN112456938A (en) * | 2020-12-10 | 2021-03-09 | 上海阳森精细化工有限公司 | High-fluidity long-operation-period polyurethane urea cement concrete mortar terrace |
| CN112521719A (en) * | 2020-12-03 | 2021-03-19 | 武汉市科达云石护理材料有限公司 | Water-based epoxy resin cement-based slurry as well as preparation method and application thereof |
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| CN111234172A (en) * | 2020-01-17 | 2020-06-05 | 阳泉煤业（集团）有限责任公司 | Epoxy resin/water glass/polyurethane composite reinforced material and preparation method thereof |
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| CN111499336B (en) * | 2020-04-30 | 2021-06-29 | 山东大学 | Cuttable material for reinforcing tunnel portal |
| CN112521719A (en) * | 2020-12-03 | 2021-03-19 | 武汉市科达云石护理材料有限公司 | Water-based epoxy resin cement-based slurry as well as preparation method and application thereof |
| CN112521719B (en) * | 2020-12-03 | 2023-10-20 | 武汉市科达云石护理材料有限公司 | Water-based epoxy resin cement-based slurry, and preparation method and application thereof |
| CN112456938A (en) * | 2020-12-10 | 2021-03-09 | 上海阳森精细化工有限公司 | High-fluidity long-operation-period polyurethane urea cement concrete mortar terrace |
| CN112456938B (en) * | 2020-12-10 | 2022-08-26 | 上海阳森精细化工有限公司 | High-fluidity long-operation-period polyurethane urea cement concrete mortar terrace |
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Application publication date: 20151230 |