CN105440651B - A kind of polyurethane injecting paste material for roadbed karst cave in bottom class damage repair - Google Patents
A kind of polyurethane injecting paste material for roadbed karst cave in bottom class damage repair Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
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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
- C08G18/36—Hydroxylated esters of higher fatty acids
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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
- C08G18/6629—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/36 or hydroxylated esters of higher fatty acids of C08G18/38
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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Abstract
Polyurethane injecting paste material of the present invention for roadbed karst cave in bottom class damage repair, raw material include by weight：60 80 parts of base polyurethane prepolymer for use as, 15 25 parts of phenol-formaldehyde resin modified, 1 10 parts of organo montmorillonite, 5 15 parts of fire retardant, 23 parts of antistatic agent, 5 30 parts of plasticizer, 2 10 parts of foam stabiliser, 0.05 1 parts of catalyst, 10 35 parts of solvent.Polyurethane injecting paste material of the present invention for roadbed karst cave in bottom class damage repair has the instant efficiency of good curing and higher dimensional stability, and excellent in mechanical performance, project durability are strong.
Description
Technical field
The present invention relates to injecting paste material technical fields more particularly to a kind of for roadbed karst cave in bottom class damage repair
Polyurethane injecting paste material.
Background technology
Roadbed karst cave in bottom because level of ground water with seasonal variations and latent erosion, vacuum suction the effects that, easily form soil cave, concurrently
It transforms into collapse or increases load due to newly-increased built-loading etc. and Upper Plate of Karst Cave is made to generate collapse.At present, solution cavity is punished
Major measure is slip casting, and the selection of wherein injecting paste material is the basic problem of Grouting engineering, and is to ensure that slurry injection technique reaches pre-
The most important factor of phase purpose is to reduce project cost, cost-effective key point.
Modern injecting paste material is broadly divided into bulk material, chemical material and is answered by what bulk material and chemical material formed
Condensation material.Wherein, chemical grouting is a new technology of project seepage controlling, is widely used in external chemical grouting water blockoff antiseepage
The fields such as roadbed maintenance reinforcing, compared with traditional cements slurry injection technique, chemical grouting has its unique advantage, can solve routine
Cement injection method is difficult to the engineering roadblock solved.Chemical grouting material has preferable concrete castability than cement grouting material, and slurry viscosity is low,
It can be injected into fine pore, and the setting time of its slurries can be adjusted by engine request, can reach gelled instantaneously sometimes, than
Relatively it is suitble to carry out leak stopping or Anti-seeping technology at the position for having circulating water.But in view of the particularity of solution cavity geology, traditional water
For mud base grouting material because of the excessive application of rapid construction demand and high early injection pulp material, early-age crack problem is more prevalent.
Polyurethane injecting paste material is a kind of novel high polymer chemical slip casting material, with permeability is good, water plugging effect is good, viscous
A variety of excellent properties such as relay is strong, have been increasingly becoming one of chemical slip casting material being most widely used, have been generally divided into hydrophilic
Property and two major class of hydrophobicity, the concretion body strength of wherein hydrophobic polyurethane injecting paste material it is big, it is impervious strong, compared to hydrophily
Polyurethane injecting paste material water reinforcement effect and project durability are more preferable.
However, the main product of hydrophobic polyurethane injecting paste material used at present also be there are problems that, main table
It is now：First, its hydrophobicity slurry material meets the choosing of water reaction rate less than hydrophily product, the instant efficiency of water blockoff is significantly lower than the latter,
Simultaneously the confidence that client selects such material has been seriously affected because possessing higher cost again；Second, polyurethane injecting paste material
Durability depend on induration intensity and dried shrinking percentage, although hydrophobicity slurry material will not as hydrophilic starch material that
Large volume is shunk after sample dehydration, but the inert organic solvents in its system still can increase the drying shrinkage of induration, equally
There are the hidden danger that engineering is leaked again；Third, the resistance to acidolysis corrosivity of slurry material induration is not good enough, it is chronically under severe geological environment and obtains
Induration is easy to premature aging degradation, increases engineering and leaks probability again.
Invention content
Based on background technology there are the problem of, the present invention proposes a kind of for roadbed karst cave in bottom class damage repair
Polyurethane injecting paste material, the polyurethane injecting paste material have the instant efficiency of good curing and higher dimensional stability, and
And excellent in mechanical performance, project durability are strong.
The present invention proposes a kind of polyurethane injecting paste material for roadbed karst cave in bottom class damage repair, and raw material is pressed
Parts by weight include：60-80 parts of base polyurethane prepolymer for use as, 15-25 parts of phenol-formaldehyde resin modified, 1-10 parts of organo montmorillonite, fire retardant 5-
15 parts, 2-3 parts of antistatic agent, 5-30 parts of plasticizer, 2-10 parts of foam stabiliser, 0.05-1 parts of catalyst, 10-35 parts of solvent；
The preparation method of the base polyurethane prepolymer for use as includes：By polyether polyol, polyester polyol and soybean oil polyol
It adds in reaction kettle, is dehydrated 2-3h under the conditions of vacuum degree is ﹣ 0.08- ﹣ 0.1MPa, temperature is 110-120 DEG C, is cooled to 55-
It 65 DEG C, is passed through nitrogen and restores normal pressure, add in polyisocyanates, in a nitrogen atmosphere after insulated and stirred 0.5-1h, be warming up to 80-90
DEG C, 2-3h is stirred to react, 50-60 DEG C is cooled to after the completion of reaction, obtains base polyurethane prepolymer for use as；Wherein, polyether polyol, polyester
Polyalcohol, soybean oil polyol, polyisocyanates weight proportion be：2-5:1-3:1-3:10-12；Preferably, the poly- ammonia
The content of the isocyano of ester performed polymer is 20-25wt%.
Preferably, the soybean oil polyol is primary hydroxyl soybean oil polyol, and preparation method includes：By epoxy soybean
Oil is added in isopropanol, and diethanol amine and tetrafluoro boric acid are added under stirring condition, 60-80 DEG C is heated to, is stirred to react 10-15h,
Decompression boils off isopropanol, is washed with saturation metabisulfite solution, filters, obtains the primary hydroxyl soybean oil polyol；Preferably, institute
The hydroxyl value for stating primary hydroxyl soybean oil polyol is 200-700mgKOH/g.
Preferably, it is 100-300mgKOH/g that the polyether polyol, which is hydroxyl value, and degree of functionality 2-4, average molecular weight are
The polyether polyol of 1000-6000；The polyester polyol is hydroxyl value for 160-240mgKOH/g, degree of functionality 2-3, average mark
Polyester polyol of the son amount for 1000-4000.
Preferably, the phenol-formaldehyde resin modified is to first by weight by 100 parts of phenol, 10-20 parts of lignin and 1-5 parts
2-8h is reacted at 100-150 DEG C after the mixing of base benzene sulfonic acid, 50-100 parts of formaldehyde, 2-20 parts of potassium hydroxide are added in, in 60-100
1-5h is reacted at DEG C and obtains dope, is dehydrated, is dried to obtain after the dope is washed 2-5 times with 60-70 DEG C of water.
Preferably, the fire retardant is tricresyl phosphate (β-chloroethyl) ester；The antistatic agent resists for quaternary ammonium salt polyurethane
Electrostatic agent.
Preferably, the plasticizer is that dioctyl phthalate, dinonyl phthalate, phthalic acid two are different
One or more mixtures in nonyl ester, diisooctyl phthalate；The foam stabiliser is polyether-modified poly- silica
One kind of multiple mixtures in alkane, polyvinylpyrrolidone, Tween 80；The solvent is acetone, butanone, toluene, two
One or more mixtures in toluene, ethyl acetate.
Preferably, the catalyst be by quality proportioning be 1:Tertiary amine catalyst and the organic tin catalysis of 0.15-0.3
Agent forms；Preferably, the tertiary amine catalyst is triethylamine, triethylene diamine, N- methylmorpholines and dimethyl benzylamine
In one or more mixtures, the organic tin catalyst be stannous octoate, dibutyl tin laurate and two acetic acid
One or more mixtures in dibutyl tin.
A kind of preparation method of the polyurethane injecting paste material for roadbed karst cave in bottom class damage repair, packet
It includes, phenol-formaldehyde resin modified, organo montmorillonite, fire retardant, antistatic agent, plasticizer, bubble is added in into the base polyurethane prepolymer for use as
Foam stabilizers, catalysts and solvents, stir evenly, and obtain the polyurethane for roadbed karst cave in bottom class damage repair and note
Pulp material.
Polyurethane injecting paste material of the present invention for roadbed karst cave in bottom class damage repair, by by polyether polyols
Alcohol, polyester polyol, soybean oil polyol and polyisocyanates block polymerization obtain the base polyurethane prepolymer for use as, then in tradition
Polyurethane carbon-carbon skeletal chain structure in embedded organic ether, organic ester and soybean oil polyol segment；Due to ehter bond in organic ether
Polarity is small, and hydrolytic stability is good, and alkaline resistance properties protrudes, therefore can assign the good water resistance of the slurry material after curing and ageing resistance
Energy；Introducing in organic ester can make the submissive performance enhancement of base polyurethane prepolymer for use as main chain, show as high resiliency, be embedded into poly-
In urethane main chain, the good mechanical property of the slurry material after curing and acid-proof alkaline are assigned；Soybean oil polyol contains many primary
Hydroxyl, high proportion of primary OH groups can increase the reaction rate with polyisocyanates, increase performed polymer crosslinking degree, assign slurry
The good barrier performance of material；Soybean oil polyol has very strong water imbibition simultaneously, and polyurethane injecting paste material of the present invention exists
When penetrating into roadbed karst cave in bottom by grouting pressure and the low viscosity of itself, polyurethane can be relied on after meeting water in crack is leaked
Absorption water in performed polymer in soybean oil polyol reacts rapidly foaming with water, therefore meets water and be swift in response, and can assign polyurethane
Injecting paste material has the instant efficiency of good curing, and while ensure to starch material excellent in mechanical performance with this, and dimensional stability carries
Height largely improves the acid-alkali-corrosive-resisting and project durability of product.
In addition, the present invention is also added into a certain amount of filler, plasticizer, resistance in the polyurethane injecting paste material is configured
Agent and catalyst etc. are fired, wherein filler selection adds in phenol-formaldehyde resin modified and organo montmorillonite, the phenol-formaldehyde resin modified
It is modified by lignin, not only free phenol content is relatively low, heat decomposition temperature is higher, but also toughness and intensity are higher,
It is even to be dispersed in polyurethane injecting paste material, the mechanical property of injecting paste material is not only improved, and improve injecting paste material and road surface
Cementability；The porous structure of organo montmorillonite also improves injecting paste material water suction foaming coefficient, and can enhance the resistance to of slurry material
Soda acid performance；Particular kind of catalyst choice can then adjust slurry material solidification rate, be glued between roadbed after making gel solidification
Knot property is excellent, and the polyurethane induration of formation has certain toughness, flame retardant property, with this adapt to the deformation of roadbed karst cave in bottom and
Extraneous stress influences.
Specific embodiment
The present invention is described in detail with reference to specific embodiment.
Embodiment 1
The polyurethane injecting paste material of roadbed karst cave in bottom class damage repair is used for described in the present embodiment, raw material to be by weight
Part includes：60 parts of base polyurethane prepolymer for use as, 25 parts of phenol-formaldehyde resin modified, 1 part of organo montmorillonite, tricresyl phosphate (β-chloroethyl) ester 15
Part, 2 parts of quaternary ammonium salt polyurethane electrostatic resistance agent, 30 parts of dioctyl phthalate, 2 parts of Siloxane-Oxyalkylene Copolymers, catalyst 1
Part, 10 parts of acetone；
Wherein, the preparation method of the base polyurethane prepolymer for use as includes：Polyether polyol, polyester polyol and soybean oil is more
First alcohol is added in reaction kettle, is dehydrated 2h under the conditions of vacuum degree is ﹣ 0.08MPa, temperature is 120 DEG C, is cooled to 65 DEG C, is passed through nitrogen
Gas restores normal pressure, adds in polyisocyanates, in a nitrogen atmosphere after insulated and stirred 0.5h, is warming up to 90 DEG C, is stirred to react 2h, instead
Should 60 DEG C be cooled to after the completion, obtain base polyurethane prepolymer for use as；Wherein, polyether polyol, polyester polyol, soybean oil polyol,
The weight proportion of polyisocyanates is：2:3:1:12；The soybean oil polyol be primary hydroxyl soybean oil polyol, preparation side
Method includes：Epoxidized soybean oil is added in isopropanol, diethanol amine and tetrafluoro boric acid are added under stirring condition, is heated to 60 DEG C,
15h is stirred to react, decompression boils off isopropanol, washed with saturation metabisulfite solution, filters, it is polynary to obtain the primary hydroxyl soybean oil
Alcohol, the hydroxyl value of the primary hydroxyl soybean oil polyol is 200mgKOH/g；The polyether polyol is that hydroxyl value is 300mgKOH/g,
The polyether polyol that degree of functionality is 2, average molecular weight is 6000；The polyester polyol is hydroxyl value for 160mgKOH/g, function
It is 3 to spend, and average molecular weight is 1000 polyester polyol；The content of the isocyano of the base polyurethane prepolymer for use as is 20wt%；
100 parts of phenol, 10 parts of lignin and 5 parts of p-methyl benzenesulfonic acids is are mixed by the phenol-formaldehyde resin modified by weight
8h is reacted at 100 DEG C afterwards, adds in 50 parts of formaldehyde, 20 parts of potassium hydroxide, 5h is reacted at 60 DEG C and obtains dope, with 60 DEG C of water
It is dehydrated, is dried to obtain after the dope is washed 5 times；The catalyst be by quality proportioning be 1:0.15 triethylamine and pungent
Sour stannous composition.
Embodiment 2
The polyurethane injecting paste material of roadbed karst cave in bottom class damage repair is used for described in the present embodiment, raw material to be by weight
Part includes：80 parts of base polyurethane prepolymer for use as, 15 parts of phenol-formaldehyde resin modified, 10 parts of organo montmorillonite, tricresyl phosphate (β-chloroethyl) ester 5
Part, 3 parts of quaternary ammonium salt polyurethane electrostatic resistance agent, 5 parts of dinonyl phthalate, 10 parts of polyvinylpyrrolidone, catalyst
0.05 part, 35 parts of butanone；
Wherein, the preparation method of the base polyurethane prepolymer for use as includes：Polyether polyol, polyester polyol and soybean oil is more
First alcohol is added in reaction kettle, is dehydrated 3h under the conditions of vacuum degree is ﹣ 0.1MPa, temperature is 110 DEG C, is cooled to 55 DEG C, is passed through nitrogen
Gas restores normal pressure, adds in polyisocyanates, in a nitrogen atmosphere after insulated and stirred 1h, is warming up to 80 DEG C, is stirred to react 3h, reacts
It is cooled to 50 DEG C after the completion, obtains base polyurethane prepolymer for use as；Wherein, polyether polyol, polyester polyol, soybean oil polyol, more
The weight proportion of isocyanates is：5:1:3:10；The soybean oil polyol be primary hydroxyl soybean oil polyol, preparation method
Including：Epoxidized soybean oil is added in isopropanol, diethanol amine and tetrafluoro boric acid are added under stirring condition, 80 DEG C is heated to, stirs
Reaction 10h is mixed, decompression boils off isopropanol, washed with saturation metabisulfite solution, filters, it is polynary to obtain the primary hydroxyl soybean oil
Alcohol, the hydroxyl value of the primary hydroxyl soybean oil polyol is 700mgKOH/g；The polyether polyol is that hydroxyl value is 100mgKOH/g,
Degree of functionality is 4, and average molecular weight is 1000 polyether polyol；The polyester polyol is hydroxyl value for 240mgKOH/g, function
It is 2 to spend, and average molecular weight is 4000 polyester polyol；The content of the isocyano of the base polyurethane prepolymer for use as is 25wt%；
100 parts of phenol, 20 parts of lignin and 1 part of p-methyl benzenesulfonic acid is are mixed by the phenol-formaldehyde resin modified by weight
2h is reacted at 150 DEG C afterwards, adds in 100 parts of formaldehyde, 2 parts of potassium hydroxide, 1h is reacted at 100 DEG C and obtains dope, with 70 DEG C
Water is dehydrated after the dope is washed 2 times, is dried to obtain；The catalyst be by quality proportioning be 1:0.3 triethylene two
Amine and dibutyl tin laurate composition.
Embodiment 3
The polyurethane injecting paste material of roadbed karst cave in bottom class damage repair is used for described in the present embodiment, raw material to be by weight
Part includes：70 parts of base polyurethane prepolymer for use as, 20 parts of phenol-formaldehyde resin modified, 5 parts of organo montmorillonite, tricresyl phosphate (β-chloroethyl) ester 10
Part, 2.5 parts of quaternary ammonium salt polyurethane electrostatic resistance agent, 17 parts of diisooctyl phthalate, 6 parts of Tween 80,0.5 part of catalyst,
22 parts of ethyl acetate；
Wherein, the preparation method of the base polyurethane prepolymer for use as includes：Polyether polyol, polyester polyol and soybean oil is more
First alcohol is added in reaction kettle, is dehydrated 2.5h under the conditions of vacuum degree is ﹣ 0.09MPa, temperature is 115 DEG C, is cooled to 60 DEG C, is passed through
Nitrogen restores normal pressure, adds in polyisocyanates, in a nitrogen atmosphere after insulated and stirred 0.7h, is warming up to 85 DEG C, is stirred to react
2.5h is cooled to 55 DEG C after the completion of reaction, obtains base polyurethane prepolymer for use as；Wherein, polyether polyol, polyester polyol, soybean oil
Polyalcohol, polyisocyanates weight proportion be：3.5:2:2:11；The soybean oil polyol is polynary for primary hydroxyl soybean oil
Alcohol, preparation method include：Epoxidized soybean oil is added in isopropanol, diethanol amine and tetrafluoro boric acid are added under stirring condition,
70 DEG C are heated to, is stirred to react 12h, decompression boils off isopropanol, washed with saturation metabisulfite solution, filters, obtains the primary hydroxyl
Base soybean oil polyol；The hydroxyl value of the primary hydroxyl soybean oil polyol is 400mgKOH/g；The polyether polyol is hydroxyl value
For 200mgKOH/g, the polyether polyol that degree of functionality 3, average molecular weight are 3500；The polyester polyol is that hydroxyl value is
200mgKOH/g, degree of functionality 3, average molecular weight are 2500 polyester polyol；The isocyano of the base polyurethane prepolymer for use as
Content be 22wt%；
100 parts of phenol, 15 parts of lignin and 3 parts of p-methyl benzenesulfonic acids is are mixed by the phenol-formaldehyde resin modified by weight
5h is reacted at 125 DEG C afterwards, adds in 75 parts of formaldehyde, 11 parts of potassium hydroxide, 3h is reacted at 80 DEG C and obtains dope, with 65 DEG C of water
It is dehydrated, is dried to obtain after the dope is washed 3 times；The catalyst be by quality proportioning be 1:0.25 N- methylmorphines
Quinoline and dibutyltin diacetate composition.
Embodiment 4
The polyurethane injecting paste material of roadbed karst cave in bottom class damage repair is used for described in the present embodiment, raw material to be by weight
Part includes：75 parts of base polyurethane prepolymer for use as, 22 parts of phenol-formaldehyde resin modified, 4 parts of organo montmorillonite, 8 parts of fire retardant, 2 parts of antistatic agent,
20 parts of plasticizer, 4 parts of foam stabiliser, 0.1 part of catalyst, 25 parts of solvent；
Wherein, the preparation method of the base polyurethane prepolymer for use as includes：Polyether polyol, polyester polyol and soybean oil is more
First alcohol is added in reaction kettle, is dehydrated 2.5h under the conditions of vacuum degree is ﹣ 0.09MPa, temperature is 110 DEG C, is cooled to 60 DEG C, is passed through
Nitrogen restores normal pressure, adds in polyisocyanates, in a nitrogen atmosphere after insulated and stirred 0.8h, is warming up to 86 DEG C, is stirred to react
2.5h is cooled to 52 DEG C after the completion of reaction, obtains base polyurethane prepolymer for use as；Wherein, polyether polyol, polyester polyol, soybean oil
Polyalcohol, polyisocyanates weight proportion be：3:2:1:11；The soybean oil polyol is primary hydroxyl soybean oil polyol,
Preparation method includes：Epoxidized soybean oil is added in isopropanol, diethanol amine and tetrafluoro boric acid, heating are added under stirring condition
To 70 DEG C, 13h is stirred to react, decompression boils off isopropanol, washed with saturation metabisulfite solution, filters, it is big to obtain the primary hydroxyl
Soya-bean oil polyalcohol, the hydroxyl value of the primary hydroxyl soybean oil polyol is 300mgKOH/g；The polyether polyol is that hydroxyl value is
250mgKOH/g, the polyether polyol that degree of functionality 3, average molecular weight are 3000；The polyester polyol is that hydroxyl value is
180mgKOH/g, degree of functionality 2.5, average molecular weight are 2000 polyester polyol；The isocyanic acid of the base polyurethane prepolymer for use as
The content of root is 23wt%；
100 parts of phenol, 12 parts of lignin and 3 parts of p-methyl benzenesulfonic acids is are mixed by the phenol-formaldehyde resin modified by weight
4h is reacted at 130 DEG C afterwards, adds in 80 parts of formaldehyde, 10 parts of potassium hydroxide, 4h is reacted at 70 DEG C and obtains dope, uses 60-70
DEG C water is dehydrated after the dope is washed 4 times, is dried to obtain；The fire retardant is tricresyl phosphate (β-chloroethyl) ester；It is described anti-
Electrostatic agent is quaternary ammonium salt polyurethane electrostatic resistance agent；The plasticizer is diisononyl phthalate, phthalic acid two is different
The mixture of last of the ten Heavenly stems ester；The foam stabiliser is Siloxane-Oxyalkylene Copolymers, the mixture in Tween 80；The solvent is first
The mixture of benzene, dimethylbenzene；The catalyst be by quality proportioning be 1:0.2 tertiary amine catalyst and organic tin catalyst
Composition, the tertiary amine catalyst are the mixture in N- methylmorpholines and dimethyl benzylamine, the organic tin catalysis
Agent is dibutyl tin laurate and the mixture of dibutyltin diacetate；
The preparation side of the polyurethane injecting paste material for roadbed karst cave in bottom class damage repair described in embodiment 1-4
Method, including：Phenol-formaldehyde resin modified, organo montmorillonite, fire retardant, antistatic agent, increasing will be added in into the base polyurethane prepolymer for use as
Agent, foam stabiliser, catalysts and solvents are moulded, are stirred evenly, are obtained described for roadbed karst cave in bottom class damage repair
Polyurethane injecting paste material.
Embodiment 1-4 is tested for the property, the results are shown in Table 1：
It is surveyed obtained by 1 embodiment 1-4 of table for the performance of the polyurethane injecting paste material of roadbed karst cave in bottom class damage repair
Test result
Polyurethane injecting paste material of the present invention for roadbed karst cave in bottom class damage repair, by by polyether polyols
Alcohol, polyester polyol, soybean oil polyol and polyisocyanates block polymerization obtain the base polyurethane prepolymer for use as, then in tradition
Polyurethane carbon-carbon skeletal chain structure in embedded organic ether, organic ester and soybean oil polyol segment；Due to ehter bond in organic ether
Polarity is small, and hydrolytic stability is good, and alkaline resistance properties protrudes, therefore can assign the good water resistance of the slurry material after curing and ageing resistance
Energy；Introducing in organic ester can make the submissive performance enhancement of base polyurethane prepolymer for use as main chain, show as high resiliency, be embedded into poly-
In urethane main chain, the good mechanical property of the slurry material after curing and acid-proof alkaline are assigned；Soybean oil polyol contains many primary
Hydroxyl, high proportion of primary OH groups can increase the reaction rate with polyisocyanates, increase performed polymer crosslinking degree, assign slurry
The good barrier performance of material；Soybean oil polyol has very strong water imbibition simultaneously, and polyurethane injecting paste material of the present invention exists
When penetrating into roadbed karst cave in bottom by grouting pressure and the low viscosity of itself, polyurethane can be relied on after meeting water in crack is leaked
Absorption water in performed polymer in soybean oil polyol reacts rapidly foaming with water, therefore meets water and be swift in response, and can assign polyurethane
Injecting paste material has the instant efficiency of good curing, and while ensure to starch material excellent in mechanical performance with this, and dimensional stability carries
Height largely improves the acid-alkali-corrosive-resisting and project durability of product.
In addition, the present invention is also added into a certain amount of filler, plasticizer, resistance in the polyurethane injecting paste material is configured
Agent and catalyst etc. are fired, wherein filler selection adds in phenol-formaldehyde resin modified and organo montmorillonite, the phenol-formaldehyde resin modified
It is modified by lignin, not only free phenol content is relatively low, heat decomposition temperature is higher, but also toughness and intensity are higher,
It is even to be dispersed in polyurethane injecting paste material, the mechanical property of injecting paste material is not only improved, and improve injecting paste material and road surface
Cementability；The porous structure of organo montmorillonite also improves injecting paste material water suction foaming coefficient, and can enhance the resistance to of slurry material
Soda acid performance；Particular kind of catalyst choice can then adjust slurry material solidification rate, be glued between roadbed after making gel solidification
Knot property is excellent, and the polyurethane induration of formation has certain toughness, flame retardant property, with this adapt to the deformation of roadbed karst cave in bottom and
Extraneous stress influences.
The foregoing is only a preferred embodiment of the present invention, but protection scope of the present invention be not limited thereto,
Any one skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (6)
1. a kind of polyurethane injecting paste material for roadbed karst cave in bottom class damage repair, which is characterized in that its raw material is by weight
Amount part includes：60-80 parts of base polyurethane prepolymer for use as, 15-25 parts of phenol-formaldehyde resin modified, 1-10 parts of organo montmorillonite, fire retardant 5-15
Part, 2-3 parts of antistatic agent, 5-30 parts of plasticizer, 2-10 parts of foam stabiliser, 0.05-1 parts of catalyst, 10-35 parts of solvent；
The preparation method of the base polyurethane prepolymer for use as includes：Polyether polyol, polyester polyol and soybean oil polyol are added in
In reaction kettle, 2-3h is dehydrated under the conditions of vacuum degree is ﹣ 0.08- ﹣ 0.1MPa, temperature is 110-120 DEG C, is cooled to 55-65 DEG C,
It is passed through nitrogen and restores normal pressure, add in polyisocyanates, in a nitrogen atmosphere after insulated and stirred 0.5-1h, be warming up to 80-90 DEG C, stir
Reaction 2-3h is mixed, 50-60 DEG C is cooled to after the completion of reaction, obtains base polyurethane prepolymer for use as；Wherein, polyether polyol, polyester polyols
Alcohol, soybean oil polyol, polyisocyanates weight proportion be：2-5:1-3:1-3:10-12；The base polyurethane prepolymer for use as it is different
The content of cyanate radical is 20-25wt%；
The soybean oil polyol is primary hydroxyl soybean oil polyol, and preparation method includes：Epoxidized soybean oil is added in into isopropyl
In alcohol, diethanol amine and tetrafluoro boric acid are added under stirring condition, is heated to 60-80 DEG C, be stirred to react 10-15h, decompression boils off different
Propyl alcohol is washed with saturation metabisulfite solution, is filtered, is obtained the primary hydroxyl soybean oil polyol；The primary hydroxyl soybean oil is more
The hydroxyl value of first alcohol is 200-700mgKOH/g；
100 parts of phenol, 10-20 parts of lignin and 1-5 parts of p-methyl benzenesulfonic acids is are mixed by the phenol-formaldehyde resin modified by weight
2-8h is reacted after conjunction at 100-150 DEG C, 50-100 parts of formaldehyde, 2-20 parts of potassium hydroxide is added in, reacts 1- at 60-100 DEG C
5h obtains dope, is dehydrated, is dried to obtain after the dope is washed 2-5 times with 60-70 DEG C of water.
2. the polyurethane injecting paste material according to claim 1 for roadbed karst cave in bottom class damage repair, feature
It is, the polyether polyol is that hydroxyl value is 100-300mgKOH/g, and degree of functionality 2-4, average molecular weight is 1000-6000's
Polyether polyol；The polyester polyol is that hydroxyl value is 160-240mgKOH/g, degree of functionality 2-3, average molecular weight 1000-
4000 polyester polyol.
3. the polyurethane injecting paste material according to claim 1 or 2 for roadbed karst cave in bottom class damage repair, special
Sign is that the fire retardant is tricresyl phosphate（β-chloroethyl）Ester；The antistatic agent is quaternary ammonium salt polyurethane electrostatic resistance agent.
4. the polyurethane injecting paste material according to claim 1 or 2 for roadbed karst cave in bottom class damage repair, special
Sign is that the plasticizer is dioctyl phthalate, dinonyl phthalate, diisononyl phthalate, adjacent benzene
One or more mixtures in dioctyl phthalate diisodecyl ester；The foam stabiliser is Siloxane-Oxyalkylene Copolymers, polyethylene
One or more mixtures in base pyrrolidones, Tween 80；The solvent is acetone, butanone, toluene, dimethylbenzene, acetic acid
One or more mixtures in ethyl ester.
5. the polyurethane injecting paste material according to claim 1 or 2 for roadbed karst cave in bottom class damage repair, special
Sign is, it by quality proportioning is 1 that the catalyst, which is,:Tertiary amine catalyst and organic tin the catalyst composition of 0.15-0.3；
The tertiary amine catalyst is one or more in triethylamine, triethylene diamine, N- methylmorpholines and dimethyl benzylamine
Mixture, the organic tin catalyst be stannous octoate, dibutyl tin laurate and dibutyltin diacetate in one
Kind or a variety of mixtures.
6. a kind of polyurethane slip casting that roadbed karst cave in bottom class damage repair is used for according to claim 1-5 any one of them
The preparation method of material, which is characterized in that including adding in phenol-formaldehyde resin modified into the base polyurethane prepolymer for use as, organic illiteracy takes off
Soil, fire retardant, antistatic agent, plasticizer, foam stabiliser, catalysts and solvents, stir evenly, and obtain described for roadbed bottom
The polyurethane injecting paste material of portion's solution cavity class damage repair.
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