CN104974332B - It is a kind of to cure high-strength polyurethane plugging watertight grouting material soon without foaming - Google Patents
It is a kind of to cure high-strength polyurethane plugging watertight grouting material soon without foaming Download PDFInfo
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- 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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- 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
- C08G18/3225—Polyamines
- C08G18/3228—Polyamines acyclic
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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
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
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- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
- C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
- C08G18/4845—Polyethers containing oxyethylene units and other oxyalkylene units containing oxypropylene or higher oxyalkylene end groups
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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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6685—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
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- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
Abstract
A kind of to cure high-strength polyurethane plugging watertight grouting material soon without foaming, it is made of A, B two parts raw material：Component A includes isocyanate-monomer, isocyanate prepolymer, high hydrophobic environment-friendly plasticizer, and B component includes polyether polyol with high activity, chain extension-crosslinking agent, high hydrophobic environment-friendly plasticizer and anti-aging agent, and A, B component volume ratio are 1: 1.The polyurethane plugging watertight grouting material viscosity is low, convenient for perfusion, and with without foaming, fast cured characteristic, plugging effect is good, mechanical strength and green bond are high, and ageing-resistant performance is excellent, suitable for the fast blockage and waterproofing reinforcement of underground engineering distress in concrete.
Description
Technical field
The invention belongs to building material fields, and in particular to a kind of without the fast curing high-strength polyurethane plugging watertight grouting of foaming
Material.
Background technology
At present, treatment technology for tunnel seepage problem is more serious, ends for the end of the year 1998, more than 5000 seat of China railway in operation tunnel, overall length
2500km, wherein the tunnel for having water damage accounts for about 70%, water damage is serious 1362, accounts for about the 30% of operation tunnel, such as
The problems such as underground engineerings such as iron, underground people's air defense, underground garage also face leakage.It is wet that Tunnel Water Leakage can increase air in tunnel
Degree, be easy to cause the damage of the facilities such as rail, communication, illumination, according to railway department statistics, leaks the use of water tunnel rail
Service life is about 1/2 under normal condition.Moreover, Tunnel Water Leakage accelerates the carbonization speed of lining concrete, particularly there is corruption
The underground water of corrosion destroys the structure of concrete, so as to reduce the service life in tunnel.Meanwhile Tunnel Water Leakage reduces
Level of ground water, causes ecological environment destruction.
The regulation method of Tunnel Water Leakage is more, mainly including surface sealing method, staking completion method, grouting method, drainage
Deng.Under normal circumstances, to the antiseep object with more complete skeleton, grouting water-proof leak stopping is that quickly hand is effectively treated in one kind
Section is current most common blocking method.Among grouting liquid is poured into gap or cavity by it by grouting equipment, make its diffusion,
Gelling or curing, achieve the purpose that impervious leakage-stopping, it is ensured that the water resistance of waterproofing work.This method can make rift defect be closed and it is extensive
Multiple globality, by the selection of grouting material, can play the role of leak stopping and reinforcement to concrete defect, with surface sealing method and
Staking completion method is compared, its waterproof effect is more efficient, the repairing of leakage particularly larger to hydraulic pressure and water percolating capacity, can
Quickly satisfied effect is obtained, therefore the method has been widely used in renovating Tunnel Water Leakage, construct treatment technology for tunnel seepage first
Water-proof wire.
Grouting leak-stopping waterproof material includes inorganic grouting material and organic polymer grouting material.Inorganic grouting material is with water
Based on glass paste material, using earliest, and source is wide, type is more, price is low, concrete castability is good, less toxic or non-toxic, but its mechanics
Performance can not show a candle to organic polymer grouting material.Organic polymer grouting material mainly includes the third solidifying class, first coagulates class, modified epoxy
Class and polyurethanes etc., they occupy considerable status and effect in water conservancy civil engineering construction is built, be at present most
Common grouting leak-stopping material.Third it is solidifying be by acrylamide, crosslinking agent methylene diacrylamide (MBA) and water soluble oxidized-and also
Former initiation system composition, its each component are dissolved in water, and for total concentration up to 20%, slurry viscosity is small, is 1.2mPas, and solidifying
It is remained unchanged always before glue, there is good permeability, the crack of below 0.1mm can be poured into.Meanwhile third gel coagulate after water suction into
Glue expands, and has some strength, suitable for water environment, available for sealing.But acrylamide monomer is that tool is virose,
By it is many experiment be proved to be a kind of carcinogen, so third coagulate foreign countries be prohibited from using already, and gelinite compression strength
It is low, generally 0.4~0.6MPa, while there are the wet drying shrinkage that rises for colloid, salt tolerance, low-temperature flexibility and freeze-thaw resistance are poor to ask
Topic.It is using methacrylate as host agent, with being prepared with auxiliary agents such as oil-soluble initiator, accelerating agent, toughener that first, which is coagulated,.It
Monomer viscosity be only 0.69mPas, the crack of 0.05mm wide can be poured into.Slurry material compression strength after curing is high, reachable
90MPa.But first coagulate slurry material be it is grout curing shrink big and strong to water sensitivity, can not make in the case of very moist
With which has limited its applications in terms of tunnel leak stopping.Modified epoxy class grouting liquid overcomes epoxy resin to a certain extent
The shortcomings that submersible ability is relatively low and slurries heat release is big improves the compression strength of induration, shock strength, heat resistance and resistance to
Corrosive nature.But modified epoxy class grouting liquid curing rate is slower, can not quick blocking crack-leakage water, and and concrete
Damping interface adhesion strength is poor, and plugging effect is limited.Polyurethane grouting material is that the one kind to grow up the seventies is high-effect
Grouting material can play reinforcing, leak stopping, water blockoff, antiseepage in civil engineering.Polyurethane chemical grouting material activity is big and wet
Adhesion strength is higher, blocks strong water burst and the effect of flowing water in ground is prevented to protrude, and is current most widely used waterproof
Plugging material.
Common polyurethane plugging watertight grouting material mainly includes oil-soluble polyurathamc and the water-soluble poly- ammonia that foams
Ester.Oil-soluble polyurathamc is solvent type, and the country is commonly called as " cyanogen coagulates ", it is mostly by isocyanates and propylene oxide polyether polyol
The performed polymer of preparation is formulated with organic solvent and auxiliary agent.The prepolymer of water-soluble polyurathamc is by isocyanates and high EO
Active hydrogen oligomer based on content polyether polyol is prepared, can self-dispersing, emulsification after chance water.When they are by high pressure
When being injected into distress in concrete, reaction can be crosslinked by meeting water, discharged great amount of carbon dioxide gas, generated secondary osmotic pressure, high pressure
Elastomer is pressed into and is full of with secondary osmotic pressure and had the gap by thrust, reaches waterproof leak-stopping purpose.Water-soluble polyurathamc slurry
Price is low, small toxicity, packet water are big, the radius of permeability formation is big, is suitable for the dynamic stifled water burst on water stratum and soil property superficial layer
Protection etc..Chinese patent 201010599616.2《One pack system waterborne polyurethane grouting material and its raw material and preparation method》
With Chinese patent 201110337328.9《A kind of preparation method of water-expandable single-component polyurethane sealant》Using hydrophilic
Property polyethers is prepared for aqueous foaming polyurethane.But there are a large amount of EO groups on hydrophilic polyether polyol molecule chain, shape after foaming
Into induration substantially without mechanical strength, and easily by water erosion, wet and heat ageing resistant performance, anti-hydrolytic performance and alkaline resistance properties are very
Difference, it is easy dusting, scaling-off, it is vulnerable in a short time.Therefore, more preferably oiliness foaming is poly- for people's selection mechanical strength and adhesion strength
Urethane substitutes aqueous foaming polyurethane or is used cooperatively with it, carries out the closure of percolating water.Chinese patent 201010597827.7
《One pack system oil soluble polyurethane grouting material and its raw material and preparation method》With Chinese patent 200810052170.9《Poly- ammonia
Ester chemical grouting material and preparation method》Oiliness blown polyurethane materials are prepared for using non-hydrophilic polyethers.Oiliness foaming is poly-
Although the comprehensive performance of urethane is better than soluble polyurethane, leak stopping mode is still foaming and intumescing leak stopping, and the foaming of formation is consolidated
Knot body mechanical strength and ageing-resistant performance are still poor, and there are uncontrollability, cracks for the foamable reaction of oiliness polyurathamc
Local expansion ratio more than middle water is high, and abscess-size is big, and material fragility is big, and the local reaction speed for there be not water does not cure even slowly,
Especially one-component polyurathamc.In addition, being porous structure inside foaming induration, anti-permeability performance is poor, itself is easily saturating
Water, and be discontinuous bonding with concrete interface, adhesion strength is low, easily generates gap, causes secondary seepage.Oiliness foaming is poly-
The service life of urethane is generally 3~9 months, and when seeping water serious position use, its service life is even lower than 1 month.
In conclusion foaming type polyurethane plugging material is only used as closure crack-leakage water, can not play long-term
The effect of waterproof and reinforced concrete.Therefore, it is necessary to a kind of excellent without foaming, mechanical strength and adhesion strength height, endurance quality
New polyurethane plugging watertight grouting material substitution foaming type polyurethane plugging material, solves distress in concrete leakage problem,
And play the role of long-term waterproof and reinforcing concrete.
Invention content
Goal of the invention：It is an object of the present invention to solve the deficiency of the existing technology and provide a kind of with fast solid without foaming
Change high-strength polyurethane plugging watertight grouting material.
Technical solution：In order to achieve the goal above, the present invention provides a kind of without the fast curing high-strength polyurethane leak stopping of foaming
Water-proof grouting agent, the material are made of A, B two parts, and part A is made of the raw material of following masses number：Isocyanate-monomer
30~60 parts, 5~15 parts of isocyanate prepolymer, high 30~55 parts of hydrophobic environment-friendly plasticizer；Part B is by following masses number
Raw material forms：50~70 parts of polyether polyol with high activity, 5~10 parts of chain extension-crosslinking agent, height are surged 20~40 parts of environment-friendly plasticizer,
0.1~1 part of anti-aging agent；A, the two-part volume ratios of B are 1: 1.
Above-mentioned isocyanate-monomer is one or more of PAPI, Carbodiimide-Modified MDI and MDI-50.
Above-mentioned Isocyanate prepolymers body is isocyanate-monomer IPDI and the NCO content of polyols preparation 15%~20%
Prepolymer, wherein polyalcohol be molecular weight be 750~1250 erythritan, molecular weight be 1800~2000 tetrahydrochysene
Furans copolyether glycol and the Isosorbide-5-Nitrae that molecular weight is 400~1500 it is cis-/Isosorbide-5-Nitrae is trans-/1,2- vinyl mass ratio is 12~19/
One or more of 16~23/65 end hydroxy butadiene.
Above-mentioned height surges environment-friendly plasticizer as plant oil base plasticizer, citric acid ester plasticizer and fatty acid ester increasing
Mould one or more of agent.
Above-mentioned polyether polyol with high activity be tetra functional hydroxyl value be 450~650mgKOH/g polyoxypropylene and
Three-functionality-degree hydroxyl value is the one or two of the polyoxypropylene of 475~585mgKOH/g.
Above-mentioned chain extension-crosslinking agent is the Sucrose polyethers polyalcohol of 2 methyl pentamethylenediamine, diglycol and seven degrees of functionality
One or more of；Anti-aging agent is one or more of biocide mildewcide, antioxidant and hydrolysis stabilizer.
A kind of preparation method of above-mentioned polyurethane plugging watertight grouting material is that erythritan, tetrahydrofuran is common
Polyetherdiol and end hydroxy butadiene are added according to mass ratio 0.5~1: 3: 0.2~0.5 into reaction kettle, are added while stirring
Heat is to (115 ± 5) DEG C, and after vacuum dehydration 3h, mixing dihydric alcohol oligomer is retained in cooling；By isocyanate-monomer IPDI add in
(80 ± 5) DEG C in reaction kettle, are heated to, dewatered mixing dihydric alcohol oligomer is slowly added dropwise, dihydric alcohol will be mixed after 1.5h
Oligomer, which drops evenly, to be finished, the reaction was continued 1h, tests prepolymer isocyanate content, will be pre- if meeting design requirement
Near 50 DEG C of polymers temperature is hereinafter, the reaction was continued if being unsatisfactory for, and when temperature is less than 50 DEG C near, retains prepolymer；It will be pre-
Poly-, isocyanate-monomer (PAPI, carbodiimides and MDI-50) and height environment-friendly plasticizer of surging are added in into reaction kettle, vacuum
After stirring deaeration 1h, discharge up to component A；By tetra functional polyoxypropylene and three-functionality-degree polyoxypropylene according to matter
Amount is added in than 1: 2~4 into reaction kettle, is heated to while stirring (115 ± 5) DEG C, after vacuum dehydration 3h, high activity polyether is more
After first alcohol mixed liquor is cooled to less than 60 DEG C, add in chain extension-crosslinking agent, height is surged environment-friendly plasticizer and anti-aging agent, be stirred under vacuum de-
After steeping 1h, discharge up to B component.
A kind of two-part volume ratio of A, B of above-mentioned polyurethane plugging watertight grouting material is 1: 1, by A, B during use
It is in 1: 1 special slip casting machine that component, which is added in discharging volume ratio, is directly in the milk；The polyurethane plugging watertight grouting material
Slip casting error inclusiveness it is preferable, when A, B two parts volume ratio are in the range of 1: 0.9~1.1, the mechanical property of material is basic
It remains unchanged.
Working mechanism：Polyether polyol with high activity in the polyurethane plugging watertight grouting material B component is polyfunctionality
The polyether polyol of low molecular weight, its reactivity is high, and excellent reactivity can be kept without catalyst, inhibits foaming
Effect is apparent.Moreover, the polyurethane induration crosslink density that it is prepared is higher, mechanical strength is good.Meanwhile its viscosity is low, just
In mortar depositing construction.Plasticizer selects the asepsis environment-protecting plasticizer of non-neighboring benzene class, and water content is extremely low (≤0.05%), itself hydrophobic
It is with obvious effects, moisture can be obstructed and enter material internal.Moreover, it is preferable with such polyethers conformability, it is tough material can be effectively improved
Property, even if incorporation is larger will not to there is the problems such as being precipitated, bleed.In order to avoid polyurethane plugging watertight grouting material rigidity
Excessive, cure shrinkage problems of crack has used aliphatic isocyanates IPDI and erythritan, tetrahydrochysene furan in component A
It mutters prepolymer prepared by copolyether glycol and end hydroxy butadiene, it can be effectively improved polyurethane plugging watertight grouting material
Comprehensive mechanical property, the features such as making it have High-tenacity high-strength.Meanwhile three kinds of specific dihydric alcohol oligomer mix according to a certain percentage
It is relatively low to close the prepolymer viscosity prepared, low temperature nodeless mesh.Moreover, it surges with isocyanate-monomer and height, environment-friendly plasticizer is compatible
Property is good, can prepare the component A of viscosity≤50mPas.
Advantageous effect：It is provided by the invention a kind of without the fast curing high-strength polyurethane plugging watertight grouting material of foaming, pass through
A large number of experiments is studied, and each component proportioning of the component is scientific and reasonable, and the composition has following excellent performance：
(1) it is convenient to construct：Polyurethane plugging watertight grouting material A, B component volume ratio for 1: 1, two-component note can be used
The direct slip casting of pulp grinder, and A, B component volume ratio be 1: 0.9~1.1 when, induration performance is essentially identical, can be neglected construction
When slip casting machine and personnel operation caused by error.
(2) concrete castability is excellent：Polyurethane plugging watertight grouting material viscosity≤50mPas (generally 150mPas with
On), gap can be filled up in a short time.
(3) closure and good water-proof effect：Polyurethane plugging watertight grouting material in water split by setting time≤4min, injection
After seam, quickly leak can be blocked, and induration is closely knit, it is internal and with bubble-free at concrete binding, itself is not under hydraulic pressure
It is permeable.
(3) mechanical strength height, good toughness：Polyurethane plugging watertight grouting material 7d compression strength >=25MPa, tensile strength
>=15MPa, elongation at break >=20% can be used as long-term waterproofing reinforcement materials'use.
(4) adhesion strength is high：Polyurethane plugging watertight grouting material bonds closely with concrete damping interface, and wet bonding is strong
Degree >=1.5MPa, when bearing higher hydraulic pressure, material will not degumming leak.
(5) stability is good：Cure shrinkage≤2%, will not it is too fast because of curing rate, shrink it is excessive caused by material itself
Cracking is opened, and the water quality such as saliferous, alkali () are to polyurethane plugging watertight grouting material curing rate with concrete binding emaciated face
It is not influenced substantially with adhesive property etc..
(6) ageing-resistant performance is good：Wet and heat ageing resistant, alkaline-resisting and resistance to salting liquid are had excellent performance, after burin-in process, material
Tensile strength and compression strength change rate≤5%.
Specific embodiment
Specific embodiment is illustrated with embodiment below, these embodiments are only limitted to illustrate the present invention, without limiting
The scope of the present invention.
Embodiment 1
Component A：
By erythritan, tetrahydrofuran copolyether glycol and end hydroxy butadiene according to mass ratio 0.5: 3: 0.2
It adds in into reaction kettle, is heated to while stirring (115 ± 5) DEG C, after vacuum dehydration 3h, it is oligomeric that mixing dihydric alcohol is retained in cooling
Object；Isocyanate-monomer IPDI is added in into reaction kettle, is heated to (80 ± 5) DEG C, dewatered mixing binary is slowly added dropwise
Mixing dihydric alcohol oligomer is dropped evenly after 1.5h and finished by alcohol oligomer, is reacted to prepolymer isocyanate content and is
When 20%, stop reaction, by near less than the 50 DEG C retentions of prepolymer temperature.By 15 parts of prepolymers, 30 parts of PAPI, 25 parts of vegetable oil
Base plasticizer and 30 parts of citric acid ester plasticizers are added in into reaction kettle, after being stirred under vacuum deaeration 1h, are discharged up to component A.
B component：
10 parts of tetra functional polyoxypropylenes and 40 parts of three-functionality-degree polyoxypropylenes are added in into reaction kettle, side
Stirring side be heated to (115 ± 5) DEG C, after vacuum dehydration 3h, by polyether polyol with high activity mixed liquor be cooled to 60 DEG C hereinafter, plus
Enter 5 parts of 2 methyl pentamethylenediamines, 40 parts of fatty acid ester plasticisers, 0.4 part of biocide mildewcide, 0.2 part of antioxidant and 0.4 part of hydrolysis
Stabilizer after being stirred under vacuum deaeration 1h, discharges up to B component.
A, the volume ratio of two components of B is 1: 1.
Embodiment 2
Component A：
Erythritan, tetrahydrofuran copolyether glycol and end hydroxy butadiene are added according to mass ratio 1: 3: 0.5
Enter into reaction kettle, be heated to while stirring (115 ± 5) DEG C, after vacuum dehydration 3h, mixing dihydric alcohol oligomer is retained in cooling；
Isocyanate-monomer IPDI is added in into reaction kettle, is heated to (80 ± 5) DEG C, it is low that dewatered mixing dihydric alcohol is slowly added dropwise
Mixing dihydric alcohol oligomer is dropped evenly after 1.5h and finished by polymers, and it is 15% to react to prepolymer isocyanate content
When, stop reaction, by near less than the 50 DEG C retentions of prepolymer temperature.By 5 parts of prepolymers, 60 parts of Carbodiimide-Modified MDI and
30 parts of fatty acid ester plasticisers are added in into reaction kettle, after being stirred under vacuum deaeration 1h, are discharged up to component A.
B component：
23 parts of tetra functional polyoxypropylenes and 47 parts of three-functionality-degree polyoxypropylenes are added in into reaction kettle, side
Stirring side be heated to (115 ± 5) DEG C, after vacuum dehydration 3h, by polyether polyol with high activity mixed liquor be cooled to 60 DEG C hereinafter, plus
Enter 8 parts of diglycols, the Sucrose polyethers polyalcohol of 2 part of seven degree of functionality, 20 parts of citric acid ester plasticizers, 0.04 part of sterilization
Mould inhibitor, 0.02 part of antioxidant and 0.04 part of hydrolysis stabilizer after being stirred under vacuum deaeration 1h, discharge up to B component.
A, the volume ratio of two components of B is 1: 1.
Embodiment 3
Component A：
By erythritan, tetrahydrofuran copolyether glycol and end hydroxy butadiene according to mass ratio 0.75: 3:
0.35 adds in into reaction kettle, is heated to while stirring (115 ± 5) DEG C, and after vacuum dehydration 3h, it is low that mixing dihydric alcohol is retained in cooling
Polymers；Isocyanate-monomer IPDI is added in into reaction kettle, is heated to (80 ± 5) DEG C, dewatered mixing two is slowly added dropwise
Mixing dihydric alcohol oligomer is dropped evenly after 1.5h and finished, reacted to prepolymer isocyanate content by first alcohol oligomer
When being 17.5%, stop reaction, by near less than the 50 DEG C retentions of prepolymer temperature.By 10 parts of prepolymers, 45 parts of MDI-50,22.5
Part plant oil base plasticizer and 20 parts of fatty acid ester plasticisers are added in into reaction kettle, and after being stirred under vacuum deaeration 1h, discharging is
Obtain component A.
B component：
16 parts of tetra functional polyoxypropylenes and 44 parts of three-functionality-degree polyoxypropylenes are added in into reaction kettle, side
Stirring side be heated to (115 ± 5) DEG C, after vacuum dehydration 3h, by polyether polyol with high activity mixed liquor be cooled to 60 DEG C hereinafter, plus
Enter 6 parts of 2 methyl pentamethylenediamines, the Sucrose polyethers polyalcohol of 1.5 part of seven degree of functionality, 30 parts of fatty acid ester plasticisers, 0.1 part kill
Bacterium mould inhibitor, 0.2 part of antioxidant and 0.25 part of hydrolysis stabilizer after being stirred under vacuum deaeration 1h, discharge up to B component.
A, the volume ratio of two components of B is 1: 1.
Embodiment 4
Component A：
By erythritan, tetrahydrofuran copolyether glycol and end hydroxy butadiene according to mass ratio 0.6: 3: 0.3
It adds in into reaction kettle, is heated to while stirring (115 ± 5) DEG C, after vacuum dehydration 3h, it is oligomeric that mixing dihydric alcohol is retained in cooling
Object；Isocyanate-monomer IPDI is added in into reaction kettle, is heated to (80 ± 5) DEG C, dewatered mixing binary is slowly added dropwise
Mixing dihydric alcohol oligomer is dropped evenly after 1.5h and finished by alcohol oligomer, is reacted to prepolymer isocyanate content and is
When 16%, stop reaction, by near less than the 50 DEG C retentions of prepolymer temperature.By 7.5 parts of prepolymers, 10 parts of PAPI, 27.5 parts
MDI-50,17 parts of citric acid ester plasticizers and 20 parts of plant oil base plasticizer are added in into reaction kettle, are stirred under vacuum deaeration 1h
Afterwards, it discharges up to component A.
B component：
13 parts of tetra functional polyoxypropylenes and 42 parts of three-functionality-degree polyoxypropylenes are added in into reaction kettle, side
Stirring side be heated to (115 ± 5) DEG C, after vacuum dehydration 3h, by polyether polyol with high activity mixed liquor be cooled to 60 DEG C hereinafter, plus
Enter 2 parts of 2 methyl pentamethylenediamines, 3 parts of diglycols, the Sucrose polyethers polyalcohol of 1 part of seven degree of functionality, 15 parts of plant oil bases to increase
Mould agent, 10 parts of fatty acid ester plasticisers, 0.1 part of biocide mildewcide, 0.1 part of antioxidant and 0.05 part of hydrolysis stabilizer, vacuum
After stirring deaeration 1h, discharge up to B component.
A, the volume ratio of two components of B is 1: 1.
Embodiment 5
Component A：
By erythritan, tetrahydrofuran copolyether glycol and end hydroxy butadiene according to mass ratio 0.9: 3: 0.4
It adds in into reaction kettle, is heated to while stirring (115 ± 5) DEG C, after vacuum dehydration 3h, it is oligomeric that mixing dihydric alcohol is retained in cooling
Object；Isocyanate-monomer IPDI is added in into reaction kettle, is heated to (80 ± 5) DEG C, dewatered mixing binary is slowly added dropwise
Mixing dihydric alcohol oligomer is dropped evenly after 1.5h and finished by alcohol oligomer, is reacted to prepolymer isocyanate content and is
When 19%, stop reaction, by near less than the 50 DEG C retentions of prepolymer temperature.By 12.5 parts of prepolymers, 30 parts of PAPI, 21 parts of carbonizations
Diimine is modified MDI, 20 parts of fatty acid ester plasticisers and 29 parts of plant oil base plasticizer and adds in into reaction kettle, is stirred under vacuum
After deaeration 1h, discharge up to component A.
B component：
20 parts of tetra functional polyoxypropylenes and 45 parts of three-functionality-degree polyoxypropylenes are added in into reaction kettle, side
Stirring side be heated to (115 ± 5) DEG C, after vacuum dehydration 3h, by polyether polyol with high activity mixed liquor be cooled to 60 DEG C hereinafter, plus
Enter 3 parts of 2 methyl pentamethylenediamines, 4.5 parts of diglycols, 1 part of seven degree of functionality Sucrose polyethers polyalcohol, 35 fatty acid esters
Plasticizer, 0.3 part of biocide mildewcide, 0.2 part of antioxidant and 0.25 part of hydrolysis stabilizer, after being stirred under vacuum deaeration 1h, discharging is
Obtain B component.
A, the volume ratio of two components of B is 1: 1.
Embodiment 6
Component A：
By erythritan, tetrahydrofuran copolyether glycol and end hydroxy butadiene according to mass ratio 0.8: 3: 0.3
It adds in into reaction kettle, is heated to while stirring (115 ± 5) DEG C, after vacuum dehydration 3h, it is oligomeric that mixing dihydric alcohol is retained in cooling
Object；Isocyanate-monomer IPDI is added in into reaction kettle, is heated to (80 ± 5) DEG C, dewatered mixing binary is slowly added dropwise
Mixing dihydric alcohol oligomer is dropped evenly after 1.5h and finished by alcohol oligomer, is reacted to prepolymer isocyanate content and is
When 18%, stop reaction, by near less than the 50 DEG C retentions of prepolymer temperature.By 11 parts of prepolymers, 15 parts of MDI-50,25 parts of carbonizations
Diimine is modified MDI, 20 parts of plant oil base plasticizer and 31 parts of citric acid ester plasticizers and adds in into reaction kettle, is stirred under vacuum
After deaeration 1h, discharge up to component A.
B component：
18 parts of tetra functional polyoxypropylenes and 44 parts of three-functionality-degree polyoxypropylenes are added in into reaction kettle, side
Stirring side be heated to (115 ± 5) DEG C, after vacuum dehydration 3h, by polyether polyol with high activity mixed liquor be cooled to 60 DEG C hereinafter, plus
Enter 2 parts of 2 methyl pentamethylenediamines, 2.5 parts of diglycols, 1 part of seven degree of functionality Sucrose polyethers polyalcohol, 28 parts of aliphatic esters
Class plasticizer, 0.3 part of biocide mildewcide, 0.2 part of antioxidant and 0.1 part of hydrolysis stabilizer, after being stirred under vacuum deaeration 1h, discharging is
Obtain B component.
A, the volume ratio of two components of B is 1: 1.
Dual-component polyurethane plugging watertight grouting material result of the test is as shown in the table in example 1~6：
Claims (6)
- It is 1. a kind of without the fast curing high-strength polyurethane plugging watertight grouting material of foaming, it is characterised in that：The material is by A, B two parts Composition, part A are made of the raw material of following masses number：30~60 parts of isocyanate-monomer, isocyanate prepolymer 5~15 Part, the isocyanate prepolymer for NCO content prepared by isocyanate-monomer IPDI and dihydric alcohol oligomer 15%~ 20% prepolymer, wherein dihydric alcohol oligomer be molecular weight be 750~1250 erythritan, molecular weight be 1800~ Isosorbide-5-Nitrae that 2000 tetrahydrofuran copolyether glycol and molecular weight is 400~1500 is cis-/and Isosorbide-5-Nitrae is trans-/1,2- vinyl mass ratioes For 12~19/16~23/65 one or more of end hydroxy butadiene, 30~55 parts of low water content environment-friendly plasticizer, The low water content environment-friendly plasticizer is the environment-friendly plasticizer of water content≤0.05%；Part B by following masses number raw material Composition：50~70 parts of polyether polyol with high activity, the polyether polyol with high activity be tetra functional hydroxyl value be 450~ The polyoxypropylene and three-functionality-degree hydroxyl value of 650mgKOH/g be 475~585mgKOH/g polyoxypropylene one kind or Two kinds, 5~10 parts of chain extension-crosslinking agent, 20~40 parts of low water content environment-friendly plasticizer, 0.1~1 part of anti-aging agent；A, B is two-part Volume ratio is 1: 0.9~1.1.
- 2. according to claim 1 a kind of without the fast curing high-strength polyurethane plugging watertight grouting material of foaming, feature exists In：The isocyanate-monomer is one or more of PAPI, Carbodiimide-Modified MDI and MDI-50.
- 3. according to claim 1 a kind of without the fast curing high-strength polyurethane plugging watertight grouting material of foaming, feature exists In：The low water content environment-friendly plasticizer is plant oil base plasticizer, citric acid ester plasticizer and fatty acid ester plasticiser One or more of.
- 4. according to claim 1 a kind of without the fast curing high-strength polyurethane plugging watertight grouting material of foaming, feature exists In：The chain extension-crosslinking agent is 2 methyl pentamethylenediamine, one in the Sucrose polyethers polyalcohol of diglycol and seven degrees of functionality Kind is several.
- 5. according to claim 1 a kind of without the fast curing high-strength polyurethane plugging watertight grouting material of foaming, feature exists In：The anti-aging agent is one or more of biocide mildewcide, antioxidant and hydrolysis stabilizer.
- It is 6. a kind of without the fast curing high-strength polyurethane plugging watertight grouting material of foaming according to Claims 1 to 5 any one of them Preparation method, it is characterised in that：By erythritan, tetrahydrofuran copolyether glycol and end hydroxy butadiene according to matter Amount is added in than 0.5~1: 3: 0.2~0.5 in reaction kettle, being heated to 115 ± 5 DEG C while stirring, after vacuum dehydration 3h, cooling Retain mixing dihydric alcohol oligomer；Isocyanate-monomer IPDI is added in into reaction kettle, 80 ± 5 DEG C is heated to, is slowly added dropwise It is dewatered to mix dihydric alcohol oligomer, mixing dihydric alcohol oligomer is dropped evenly after 1.5h and is finished, the reaction was continued 1h, test Prepolymer isocyanate content, if meeting design requirement by prepolymer temperature be down to 50 DEG C hereinafter, if being unsatisfactory for after Continuous reaction when temperature is down to below 50 DEG C, retains prepolymer；Prepolymer, isocyanate-monomer and low water content environmental protection are increased Modeling agent is added in into reaction kettle, after being stirred under vacuum deaeration 1h, is discharged up to component A；By tetra functional polyoxypropylene and three Degree of functionality polyoxypropylene is added according to mass ratio 1: 2~4 into reaction kettle, is heated to 115 ± 5 DEG C while stirring, vacuum After being dehydrated 3h, after polyether polyol with high activity mixed liquor is cooled to less than 60 DEG C, chain extension-crosslinking agent, low water content environmental protection are added in Plasticizer and anti-aging agent after being stirred under vacuum deaeration 1h, discharge up to B component.
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| CN106674481B (en) * | 2016-11-17 | 2019-06-04 | 中国人民解放军61489部队 | A kind of extremely frigid zones concrete works polyurethane foam injecting paste material and method |
| PL3551426T3 (en) | 2016-12-06 | 2022-07-11 | Chromatic 3D Materials Inc. | Manufacture of three dimensional objects from thermosetting resins |
| CN106589283A (en) * | 2016-12-07 | 2017-04-26 | 江苏卓美聚氨酯科技有限公司 | Rigid polyurethane reinforced grouting material and preparation method thereof |
| CN106632984A (en) * | 2016-12-21 | 2017-05-10 | 中国铁道科学研究院铁道建筑研究所 | High-speed railway ballast track ballast bed surface cementing material |
| CN108659201A (en) * | 2018-06-08 | 2018-10-16 | 北京中煤矿山工程有限公司 | Anti- well drilling machine reaming construction broken formation gib material |
| CN109233258A (en) * | 2018-07-05 | 2019-01-18 | 王建东 | A kind of preparation method of water shutoff material |
| CN110294926A (en) * | 2019-06-28 | 2019-10-01 | 江苏中路工程技术研究院有限公司 | A kind of silicane-modified polyurethane material and its preparation method and application method |
| CN111217978A (en) * | 2020-03-26 | 2020-06-02 | 中煤科工集团重庆研究院有限公司 | Method for reducing dosage of organic grouting reinforcement material polymeric MDI and product thereof |
| CN111647121A (en) * | 2020-06-12 | 2020-09-11 | 北京石油化工学院 | Preparation method of two-component polyurethane composite material for pipeline repair |
| CN112142946A (en) * | 2020-08-21 | 2020-12-29 | 煤炭科学技术研究院有限公司 | Coal mine reinforcing material prepared from vegetable oil polyalcohol and preparation method thereof |
| CN112142950A (en) * | 2020-08-21 | 2020-12-29 | 煤炭科学技术研究院有限公司 | High-performance coal mine reinforcing material and preparation method thereof |
| CN112876635B (en) * | 2021-02-05 | 2022-05-27 | 浙江鲁班建材科技股份有限公司 | Low-foaming strong-bonding elastic polyurethane grouting material and preparation method thereof |
| CN113698565B (en) * | 2021-08-19 | 2023-05-05 | 山东一诺威聚氨酯股份有限公司 | Method for reducing crystallization point of polyester type modified MDI |
| 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 |
| CN115181241A (en) * | 2022-08-26 | 2022-10-14 | 河北浩威旭光新材料科技有限公司 | Organic polymer ultralow-temperature reinforcing material for coal rock mass |
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