CN110003414A - A kind of composite high-molecular slip casting strengthening material - Google Patents
A kind of composite high-molecular slip casting strengthening material Download PDFInfo
- Publication number
- CN110003414A CN110003414A CN201910212182.1A CN201910212182A CN110003414A CN 110003414 A CN110003414 A CN 110003414A CN 201910212182 A CN201910212182 A CN 201910212182A CN 110003414 A CN110003414 A CN 110003414A
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- China
- Prior art keywords
- component
- slip casting
- strengthening material
- casting strengthening
- present
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0083—Foam properties prepared using water as the sole blowing agent
Abstract
The present invention relates to Material Fields, more particularly to a kind of composite high-molecular slip casting strengthening material.The slip casting strengthening material includes component A and B component, and the raw material of the component A includes: 70~90 parts of the first isocyanates by weight；1.5~3 parts of plasticizer；0.4~1.2 part of glycerine；0.3~0.7 part of foam stabilizer；The raw material of the B component includes: 60~80 parts of the second isocyanates by weight；20~30 parts of alkali silicate；10~20 parts of water；1~2 part of catalyst.The component A and B component volume ratio are 1:1~1:1.2.The present invention, which can improve existing polyurethane slip casting strengthening material and meet frothing percentage after water, to be difficult to control, leads to the problem of that foam is uneven, expansion ratio is high, heat of reaction is high.
Description
Technical field
The present invention relates to Material Fields, more particularly to a kind of composite high-molecular slip casting strengthening material.
Background technique
In tunnel, tunnel etc. when underground spaces engineering construction, more broken rock mass condition is often encountered, if do not adopted
It takes corresponding measure that may then cause serious engineering project disaster, causes unnecessary economic loss.At this moment note would generally be taken
The method of reinforcing is starched to handle, broken rock mass is bonded together, the globality of fragmented rock body and the peace of subsequent construction are improved
Quan Xing.
In polyurethane slip casting strengthening material among these by feat of " intensity height, light weight, caking property is good, chemical property is stable "
The advantages of and be widely used in underground engineering fragmented rock body reinforce in.But at present polyurethane material on the market still have it is larger
Defect, be allowed to be applied to well during fragmented rock body reinforces, the major defect of polyurethane has: in polyurethane grouting and reinforcing
After material encounters bright water when constructing, frothing percentage is just difficult to control, and can generate cellular polyurethane foam, so that the solid formed is strong
Degree reduces；Because non-uniform bubble can be generated when foaming, the globality of breaking surrounding rock reinforcing body then will affect；It is poly-
Urethane can release a large amount of heat when reaction, can not be applied to the reinforcing of the underground engineerings such as mine.
Summary of the invention
In view of the foregoing deficiencies of prior art, the purpose of the present invention is to provide a kind of composite high-molecular grouting and reinforcings
Material can improve existing polyurethane slip casting strengthening material and meet frothing percentage after water being difficult to control, generating that foam is uneven, foaming
The problem that multiplying power is high, heat of reaction is high.
In order to achieve the above objects and other related objects, the present invention is achieved through the following technical solutions.
One aspect of the present invention provides a kind of slip casting strengthening material, and the slip casting strengthening material includes component A and B component,
The raw material of the component A includes: by weight
The raw material of the B component includes: by weight
The component A and B component volume ratio are 1:1~1:1.2.
In certain embodiments of the present invention, first isocyanates is selected from methyl diphenylene diisocyanate, more
One of the more methyl polyisocyanates of phenyl, dicyclohexyl methyl hydride diisocyanate or a variety of combinations.
In certain embodiments of the present invention, the plasticizer is selected from phthalic acid two (2- ethyl) ethyl ester.
In certain embodiments of the present invention, the foam stabilizer is Si-C class surfactant and/or modified silicone resin
Polyethers lotion.
In certain embodiments of the present invention, second isocyanates is selected from isocyanuric acid ester, allophanate, urea
The combination of one or more of diketone.
In certain embodiments of the present invention, the alkali silicate is in sodium metasilicate, potassium silicate and lithium metasilicate
One or more combinations.
In certain embodiments of the present invention, the catalyst is selected from tertiary amine catalyst, zinc class catalyst, bismuth class and urges
One of agent, organic tin catalyst or a variety of combinations are preferably selected from triethylene diamine or pentamethyl diethylidene three
One of amine, triethyl group caproic acid bismuth, dioctyltin or dibutyltin diacetate or a variety of combinations.
Another aspect of the present invention provides a kind of formed body, is prepared by slip casting strengthening material above-mentioned.
Another aspect of the present invention provides the present invention preparation method of aforementioned formed body, comprising: component A and B component mixed,
It prepares.
Another aspect of the present invention provides a kind of slip casting strengthening material of the present invention and/or formed body of the present invention
In the reinforcing of underground engineering fragmented rock body, the application of coal mine field of reinforcement.
Specific embodiment
Inventor passes through a large amount of explorative experiments, provides a kind of composite high-molecular slip casting strengthening material, described multiple
Closing macromolecule slip casting strengthening material is a kind of not to be afraid of the polyurethane polyureas that bright water, expansion ratio are low, foam is evenly distributed, heat-resist
Urea silicate combined casting reinforcement material, composite high-molecular slip casting strengthening material of the invention are needed using polyureas silicate reaction
Water, and heat-resist feature, compensate for defect existing for polyurethane material.The strength of materials after composite curing is up to 50
~60MPa, foam are evenly distributed, and bond properties is good, and reaction temperature is lower than 90 DEG C, and it is broken to may be conveniently used various underground engineerings
The reinforcing of detritus body, and the present invention is completed on this basis.
It is broken the following detailed description of composite high-molecular slip casting strengthening material according to the present invention, preparation method and in underground engineering
Application in broken rock mass reinforcing, coal mine reinforcing.
First aspect present invention provides a kind of slip casting strengthening material, and the slip casting strengthening material includes component A and B component,
The raw material of the component A includes: by weight
The raw material of the B component includes: by weight
The component A and B component volume ratio are 1:1~1:1.2.
As preferred embodiment of the invention, the slip casting strengthening material includes component A and B component,
The raw material of the component A includes: by weight
The raw material of the B component includes: by weight
The component A and B component volume ratio are 1:1~1:1.1.
Component A of the present invention is different isocyanates from B component, is respectively intended to reaction and generates polyurethane and polyureas silicic acid
Salt.Water and preferable heat resistance and caking property are needed using polyureas silicate reaction, compensates for conventional urethane grouting and reinforcing material
The deficiency of material.Two kinds of materials meet water and keep normal frothing percentage after being mixed to form, and the bubble distribution generated is uniform, will gather
Reaction temperature also declines therewith after urea silicate addition system, and the stability of system is improved.In addition what is be added is poly-
Urea silicate compositions inherently have excellent mechanical performance, in conjunction with the advantages of polyurethane after be suitable for breaking surrounding rock body plus
Gu.Polyureas silicate compositions are formed when by solidifying and it includes the polyureas matrix of the bulbous region of silicate, with variousization
Product and water are compatible in the extreme, this is just polyureas silicate and polyurethane is compound provides possibility, and furthermore polyureas silicate is also right
Different materials and geologic structure including steel show good adhesiveness.These spherical silicate regions and conventional urethane
In conjunction with the stability that integral material can be enhanced, spheric region is to react the mistake of release carbon dioxide with water in isocyanate component
It is formed in journey.It has been found that isocyanuric acid ester has excellent heat resistance, after solidifying polyurethane reaction, thermal diffusivity is changed
It is kind, it reacts the heat released and is dispersed dilution, heat can not be accumulated, be reacted when solidifying to reduce polyurethane material
Temperature.
In slip casting strengthening material provided by the present invention, first isocyanates is selected from diphenylmethane diisocyanate
One of the more methyl polyisocyanates of ester, more phenyl, dicyclohexyl methyl hydride diisocyanate etc. or a variety of combinations.
In slip casting strengthening material provided by the present invention, the plasticizer is selected from phthalic acid two (2- ethyl) ethyl ester.
In slip casting strengthening material provided by the present invention, the foam stabilizer is Si-C class surfactant and/or modified silicon
Resin polyethers lotion.Organosilicon polymer molecule (Si-C class surfactant, modified silicone resin polyethers based on silicon oxygen bond
Lotion etc.), there are good heat-resisting quantity, electrical insulating property and anticorrosive property.The stabilizer and polyureas silicate institute shape being added
At polyureas matrix one work, reduce reaction process in whole heat release, improve composite material entirety heat resistance with it is fire-retardant
Property.Experiment discovery, when the foam stabilizer additional amount is less than 0.3 part, expansion ratio is high, foam is unevenly distributed, leakproofness
Decline；When the foam stabilizer additional amount is greater than 0.7 part, injecting paste material density is larger, thermal diffusivity is bad, anti-flammability reduces.
In slip casting strengthening material provided by the present invention, second isocyanates is selected from isocyanuric acid ester, allophanic acid
The combination of one or more of ester, urea diketone etc..
In slip casting strengthening material provided by the present invention, the alkali silicate is sodium metasilicate, potassium silicate and lithium metasilicate
Deng one of or a variety of combinations.
In slip casting strengthening material provided by the present invention, the catalyst is selected from tertiary amine catalyst, zinc class catalyst, bismuth
One of class catalyst and organic tin catalyst etc. or a variety of combinations, preferred tertiary amine catalyst are triethylene diamine
Or five methyl diethylentriamine, preferred bismuth class catalyst and zinc class catalyst include the carboxylate of bismuth and zinc, such as three second
Base caproic acid bismuth, preferred organic tin catalyst are dioctyltin or dibutyltin diacetate.
The second aspect of the present invention provides a kind of formed body, the preparation of the slip casting strengthening material as described in first aspect present invention
It obtains.
The third aspect of the present invention provides the preparation method of formed body described in second aspect of the present invention, comprising: by component A
It mixes, prepares with B component.
In the preparation method of formed body provided by the present invention, by the first isocyanates, plasticizer, glycerine and foam stabilizer
The component A that hybrid reaction obtains is polyurethane.
In the preparation method of formed body provided by the present invention, the alkali silicate and water are mixed to get alkali metal
The aqueous solution of silicate then obtains the aqueous solution for obtaining alkali silicate and the second isocyanates and catalyst hybrid reaction
The B component arrived is polyureas silicate compositions.
Component A and B component in the present invention pack stored protected from light respectively.
It is broken in underground engineering that the fourth aspect of the present invention provides aforementioned composite high-molecular slip casting strengthening material and/or formed body
Broken rock mass reinforcing, the application of coal mine field of reinforcement.
The composite high-molecular slip casting strengthening material is in the reinforcing of underground engineering fragmented rock body, the application of coal mine field of reinforcement
When, component A, B component each ingredient by becoming the liquid of both of which phase after being mixed, component A and B component press body when use
Product pumps mixed perfusion to the position to need reinforcement by biliquid than 1:1.Elder generation's mixed injection B component when perfusion, it is therefore an objective to it is broken
Existing water mixing, reduces the influence that water mixes component A in rock mass, while reducing the temperature reacted when component A mixing, B group
It dispenses and reinjects component A into after.
Due to using above technical scheme, the slip casting strengthening material has following technical advantage:
(1) polyureas silicate is first added can be with reaction of moisture existing for slip casting region itself, it is ensured that subsequent addition
The reaction of polyurethane is normally carried out.
(2) polyureas silicate has excellent heat resistance, can significantly reduce material with polyurethane material mixing and react
Temperature when solidification, this can be applied to the reinforcing of the country rocks such as mine.
(3) composite material mixing after still have excellent mechanical performance, using this it is material reinforced after, the resistance to compression of stabilization zone
Intensity meets the requirement of engineering, it is ensured that engineering safety up to 55~65MPa.
(4) preparation method of the present invention is simple, high-efficient, practical, is highly susceptible to promoting.
Illustrate embodiments of the present invention below by way of specific specific example, those skilled in the art can be by this specification
Other advantages and efficacy of the present invention can be easily understood for disclosed content.The present invention can also pass through in addition different specific realities
The mode of applying is embodied or practiced, the various details in this specification can also based on different viewpoints and application, without departing from
Various modifications or alterations are carried out under spirit of the invention.
In the following embodiments, reagent, material and the instrument used such as not special explanation, it is commercially available to obtain
?.
Embodiment 1
Composite high-molecular slip casting strengthening material described in the present embodiment includes component A and B component,
The raw material of the component A includes: by weight
The raw material of the B component includes: by weight
Component A, B component each ingredient by becoming the liquid of both of which phase, component A and B group when use after being mixed
Point by volume 1:1, the sequence of component A is by slurry filling to the position to need reinforcement after first B component.
Embodiment 2
Composite high-molecular slip casting strengthening material described in the present embodiment includes component A and B component,
The raw material of the component A includes: by weight
The raw material of the B component includes: by weight
Component A, B component each ingredient by becoming the liquid of both of which phase, component A and B group when use after being mixed
Point by volume 1:1, the sequence of component A is by slurry filling to the position to need reinforcement after first B component.
Embodiment 3
Composite high-molecular slip casting strengthening material described in the present embodiment includes component A and B component,
The raw material of the component A includes: by weight
The raw material of the B component includes: by weight
Component A, B component each ingredient by becoming the liquid of both of which phase, component A and B group when use after being mixed
Point by volume 1:1.1, the sequence of component A is by slurry filling to the position to need reinforcement after first B component.
Embodiment 4
The raw material of the B component includes: by weight
Component A, B component each ingredient by becoming the liquid of both of which phase, component A and B group when use after being mixed
Point by volume 1:1.1, the sequence of component A is by slurry filling to the position to need reinforcement after first B component.
Embodiment 5
The raw material of the B component includes: by weight
Component A, B component each ingredient by becoming the liquid of both of which phase, component A and B group when use after being mixed
Point by volume 1:1.2, the sequence of component A is by slurry filling to the position to need reinforcement after first B component.
Table 1 is the performance indicator that product of the present invention is made in embodiment 1-5
| Number | Reaction temperature (DEG C) | Concretion body strength (MPa) |
| 1 | 76 | 58.4 |
| 2 | 78 | 56.7 |
| 3 | 71 | 55.3 |
| 4 | 72 | 54.2 |
| 5 | 68 | 51.4 |
As it can be seen from table 1 the ratio with B component increases, reaction temperature is being gradually reduced, but intensity also has therewith
A degree of reduction, therefore volume ratio should control appropriately, under conditions of guaranteeing concretion body strength, reduce as far as possible
Reaction temperature.
When embodiment provides numberical range, it should be appreciated that except non-present invention is otherwise noted, two ends of each numberical range
Any one numerical value can be selected between point and two endpoints.Unless otherwise defined, the present invention used in all technologies and
Scientific term is identical as the normally understood meaning of those skilled in the art of the present technique.Except specific method, equipment used in embodiment,
Outside material, grasp and record of the invention according to those skilled in the art to the prior art can also be used and this
Any method, equipment and the material of the similar or equivalent prior art of method described in inventive embodiments, equipment, material come real
The existing present invention.
Claims (10)
1. a kind of slip casting strengthening material, the slip casting strengthening material includes component A and B component,
The raw material of the component A includes: by weight
The raw material of the B component includes: by weight
The component A and B component volume ratio are 1:1~1:1.2.
2. slip casting strengthening material as described in claim 1, which is characterized in that first isocyanates is selected from diphenyl methane
One of the more methyl polyisocyanates of diisocyanate, more phenyl, dicyclohexyl methyl hydride diisocyanate or a variety of combinations.
3. slip casting strengthening material as described in claim 1, which is characterized in that the plasticizer is selected from two (2- of phthalic acid
Ethyl) ethyl ester.
4. slip casting strengthening material as described in claim 1, which is characterized in that the foam stabilizer is Si-C class surfactant
And/or modified silicone resin polyethers lotion.
5. slip casting strengthening material as described in claim 1, which is characterized in that second isocyanates is selected from isocyanuric acid
The combination of one or more of ester, allophanate, urea diketone.
6. slip casting strengthening material as described in claim 1, which is characterized in that the alkali silicate is selected from sodium metasilicate, silicon
One of sour potassium and lithium metasilicate or a variety of combinations.
7. slip casting strengthening material as described in claim 1, which is characterized in that the catalyst is selected from tertiary amine catalyst, zinc
One of class catalyst, bismuth class catalyst, organic tin catalyst or a variety of combinations, are preferably selected from triethylene diamine or five
One of methyl diethylenetriamines, triethyl group caproic acid bismuth, dioctyltin or dibutyltin diacetate or a variety of combinations.
8. a kind of formed body is prepared by the described in any item slip casting strengthening materials of claim 1~7.
9. the preparation method of formed body as claimed in claim 8, comprising: mix component A and B component, prepare.
10. a kind of slip casting strengthening material as described in any one of claims 1 to 7 and/or formed body as claimed in claim 8
In the reinforcing of underground engineering fragmented rock body, the application of coal mine field of reinforcement.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910212182.1A CN110003414A (en) | 2019-03-20 | 2019-03-20 | A kind of composite high-molecular slip casting strengthening material |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910212182.1A CN110003414A (en) | 2019-03-20 | 2019-03-20 | A kind of composite high-molecular slip casting strengthening material |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111057365A (en) * | 2019-12-31 | 2020-04-24 | 北京中矿恒安科技有限公司 | Low-temperature organic reinforcing material and preparation method thereof |
| CN111499336A (en) * | 2020-04-30 | 2020-08-07 | 山东大学 | Cuttable material for reinforcing tunnel portal |
| CN113956648A (en) * | 2021-11-26 | 2022-01-21 | 山西凝固力新型材料股份有限公司 | High-strength silicate/polyurethane urea-based composite reinforcing material and preparation method thereof |
| CN114380970A (en) * | 2022-01-11 | 2022-04-22 | 中国矿业大学 | Organic-inorganic hybrid grouting material for foaming water shutoff and preparation process thereof |
| CN115387629A (en) * | 2022-05-20 | 2022-11-25 | 黑龙江恒建中科防水科技有限公司 | Plugging repair process for accurately treating repeated leakage |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111057365A (en) * | 2019-12-31 | 2020-04-24 | 北京中矿恒安科技有限公司 | Low-temperature organic reinforcing material and preparation method thereof |
| CN111499336A (en) * | 2020-04-30 | 2020-08-07 | 山东大学 | Cuttable material for reinforcing tunnel portal |
| CN111499336B (en) * | 2020-04-30 | 2021-06-29 | 山东大学 | Cuttable material for reinforcing tunnel portal |
| CN113956648A (en) * | 2021-11-26 | 2022-01-21 | 山西凝固力新型材料股份有限公司 | High-strength silicate/polyurethane urea-based composite reinforcing material and preparation method thereof |
| CN113956648B (en) * | 2021-11-26 | 2023-02-03 | 山西凝固力新型材料股份有限公司 | High-strength silicate/polyurethane urea-based composite reinforcing material and preparation method thereof |
| CN114380970A (en) * | 2022-01-11 | 2022-04-22 | 中国矿业大学 | Organic-inorganic hybrid grouting material for foaming water shutoff and preparation process thereof |
| CN115387629A (en) * | 2022-05-20 | 2022-11-25 | 黑龙江恒建中科防水科技有限公司 | Plugging repair process for accurately treating repeated leakage |
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