CN102911340B - Low-heat-release polyurethane grouting reinforcement material and preparation method thereof - Google Patents
Low-heat-release polyurethane grouting reinforcement material and preparation method thereof Download PDFInfo
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- CN102911340B CN102911340B CN201210395609.4A CN201210395609A CN102911340B CN 102911340 B CN102911340 B CN 102911340B CN 201210395609 A CN201210395609 A CN 201210395609A CN 102911340 B CN102911340 B CN 102911340B
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Abstract
The invention discloses a low-heat-release polyurethane grouting reinforcement material and a preparation method thereof. The low-heat-release polyurethane grouting reinforcement material comprises the following raw materials in parts by mass: 100 parts of polymer polyol, 0.5 to 3.5 parts of amine catalyst, 0.5 to 3.5 parts of tin catalyst, 1 to 4 parts of foam stabilizer, 10 to 50 parts of fire retardant, 50 to 200 parts of adhesive coumarone-indene resin and 100 to 200 parts of isocyanate, wherein the polymer polyol is polyether polyol and/or polyester polyol. The preparation method is simple, the prepared grouting reinforcement material is low in cost and high in curing speed, the reaction heat release temperature is low in the curing process, and the solidification body formed by curing has excellent physical and mechanical properties and is particularly suitable for guaranteeing safety operation under a coal mine.
Description
One, technical field
The present invention relates to a kind of polyurethane material and preparation method thereof, specifically a kind of low heat release urethane slip casting strengthening material and preparation method thereof.
Two, background technology
Urethane injecting paste material has higher compressive strength, excellent adhesive property, and there is the advantages such as good stability, concrete castability is good, the reaction times is adjustable, thereby be used widely in grouting and reinforcing field, but when it is applied to Safety of Coal Mine Production as reinforcement material, when being reaction, its shortcoming emits a large amount of heat, and thermal conductivity own is low, heat constantly gathers at material internal, material exothermic heat of reaction excess Temperature, there is serious potential safety hazard, add that itself cost is higher, therefore greatly limited its range of application.
Three, summary of the invention
The present invention aims to provide a kind of low heat release urethane slip casting strengthening material and preparation method thereof, and technical problem to be solved is reduce the exothermic temperature of urethane injecting paste material and reduce its thermal discharge, and makes its good mechanical performance, and raw materials cost is cheap.
The low heat release urethane of the present invention slip casting strengthening material, is characterized in that its raw material is configured to by mass fraction:
100 parts of polymer polyatomic alcohols, amines catalyst 0.5-3.5 part, tin class catalyzer 0.5-3.5 part, suds-stabilizing agent 1-4 part, fire retardant 10-50 part, additive coumarone-indene resin 50-200 part, isocyanic ester 100-200 part;
Described polymer polyatomic alcohol is polyether glycol and/or polyester polyol.
The functionality of described polyether glycol is 2-6, and molecular weight is 100-2000, viscosity 100-1000mPas;
The functionality of described polyester polyol is 2-4, and molecular weight is 200-3000, viscosity 500-2000mPas.
Described isocyanic ester is many methyl polyphenyl polyisocyanate, reddish-brown viscous liquid ,-NCO content 30-32wt%.
Described amines catalyst is selected from N, N '-dimethylcyclohexylamine, three vinylidene diamines, N, N, N', N', N " one or more in five methyl diethylentriamine;
Described tin class catalyzer is selected from stannous octoate or dibutyl tin laurate.
Described suds-stabilizing agent is silicone oil, is specially silicone oil AK-8805, is the non-hydrolysis-type polysiloxane-polyether copolymer of a kind of silicon-carbon bond.
Described fire retardant is selected from one or more in ammonium polyphosphate, trichloroethyl phosphate, aluminium hydroxide, dimethyl methyl phosphonate.
The preparation method of the low heat release urethane of the present invention slip casting strengthening material, comprises preparation and each unit process of two fluid grouting of pre-treatment, two components:
Described pre-treatment be by polymer polyatomic alcohol at 110-120 ℃ of vacuum-drying 1-2 hour, be cooled to seal after room temperature standby;
The preparation of described pair of component is that pretreated polymer polyatomic alcohol is mixed, and then adds successively amines catalyst, tin class catalyzer, suds-stabilizing agent, fire retardant and additive coumarone-indene resin, obtains component A after stirring; Isocyanic ester is component B;
Described two fluid grouting is to utilize Double-liquid mud-injection pump component A and B component to be injected to the ground crack needing reinforcement, set time 25-150s.
In two fluid grouting process, coutroi velocity makes component A and component B mix slip casting with the volume ratio of 3:1.
The present invention adds additive coumarone-indene resin in reaction system, for the heat that disperses to discharge with diluting reaction.The additive coumarone-indene resin using is low viscosity fluent meterial, cheap and easy to get, nontoxic non-volatile.Coumarone-indene resin adds after system as inert additwe, system viscosity reduces, concrete castability is improved, and after polyurethane reaction solidifies, intermolecular distance increases, thermal diffusivity is improved, the dilution that is dispersed of the heat that discharges of reaction, heat is difficult to accumulation, thereby has reduced core temperature when polyurethane material reaction is curing, meanwhile, cost reduces greatly.
Catalyzer in the present invention is amine and tin class composite catalyst, and amine tin class catalyst ratio is different, and polyurethane reaction set time is different, and adjustable extent set time of reinforcement material of the present invention is 25 ~ 150s.
The concrete preparation process of the present invention is as follows:
1, pre-treatment
By polymer polyatomic alcohol vacuum-drying 1 ~ 2 hour at 110 ~ 120 ℃, because polymer polyatomic alcohol ratio is easier to water suction, therefore answer sealed storage after being dried.
2, the preparation of component A
Pretreated polymer polyatomic alcohol is mixed, add successively amines catalyst, tin class catalyzer, suds-stabilizing agent and fire retardant, start agitator, fully stir it is uniformly dispersed, then add coumarone-indene resin, after mixing, obtain component A.
3, the preparation of component B
Component B is isocyanic ester, and selected isocyanic ester is many many methyl of phenyl polyisocyanates (PAPI), isocyano-content 30-32%, functionality 2.7-2.8.
4, solidify
The ratio of 3:1 is got component A and component B by volume, fully stirs it is mixed, and is then poured in mould and solidifies.
5, sample preparation
After slurry reaction has solidified, induration to be taken out from mould, room temperature is placed 3d, utilize standard hacksaw and cut-off knife, select its cured article without epidermis part, avoid bubble, crack, area of stress concentration and be cut into blockly with measured compressed intensity, batten shape is to survey tensile strength.
6, performance test
According to " colliery reinforcing coal rock mass macromolecular material " industry standard, survey its performance.
7, mixed construction
During site operation, component A and component B are annotated respectively in two charging baskets of two-pack type high-pressure grouting machine, the volume ratio of utilizing control valve to control component A and component B is 3:1, utilizes high-pressure grouting machine that two component slurries are sprayed in the grouting hole of having accomplished fluently, and mixes slip casting.After completing, slip casting utilize organic solvent to clean grout machine.
The present invention has following characteristics:
1, low viscosity.Viscosity of material of the present invention is very low, and component A and component B viscosity are all less than 500mPas, have the well property noted, and is applicable to coal and rock grouting process under coal mine;
2, low exothermicity.Material cured reaction process exothermic temperature of the present invention is less than 100 ℃, and exothermic temperature is low, is particularly suitable for the processing that under coal mine, coal and rock is reinforced, and meets the security requirement of using under coal mine;
3, environmental protection.Material of the present invention is not used volatile organic solvent, and flash-point is high, nontoxic, to the mankind and environmental friendliness;
4, compressive strength is better.Material of the present invention compressive strength after solidifying is better, can reach 7 ~ 15MPa, meets the basic demand of reinforcing fractured coal and rock under coal mine;
5, high-adhesion.Between the coal and rock of the curing Hou Yu of material gel of the present invention crack, cohesiveness is good, and the induration of formation has certain elasticity, can meet the deformation requirement of various grounds;
6, set time is adjustable.According to field condition, can regulate 25 ~ 150s set time, can adapt to the processing of various complex-terrains;
7, cost is lower.The interpolation of coumarone-indene resin can significantly reduce the cost of raw material.
The present invention compared with prior art has following advantage:
1, because the present invention has used cheap coumarone-indene resin for raw material in a large number, the production cost of material is reduced greatly, overcome the expensive shortcoming of urethane reinforcement material, for the preparation and application of such material provide Liao Hen great space.
2, adding of coumarone-indene resin, reduces the exothermic heat of reaction temperature that slurries produce in consolidation process, and maximum temperature is below 100 ℃.This mainly has benefited from adding after coumarone-indene resin, the heat that makes to discharge in the polyurethane material solidify reaction process dilution that is dispersed, and heat is difficult to accumulation, thereby has reduced the exothermic heat of reaction temperature of material.
3, in the present invention, the low property noted of the slurry viscosity of gained is good, and induration good mechanical properties, flame retardant properties are good, and raw material preparation technology and required production and construction equipment are simple, are easy to promote the use of.The set time of injection material of the present invention is adjustable from 25 ~ 150s, after slurries solidify, the compressive strength of induration can reach 7 ~ 15MPa, and ageing resistance is good, flame retardant properties good (certainly putting out from fire), and slurries flash-point is lower than 100 ℃, and fixed thing and cinder adhesive property are good.
Four, embodiment
The all reagent of the present invention and raw material are commercial.
Embodiment 1:
(1) by polyether glycol 303(functionality 3, molecular weight 350, viscosity 350 ~ 550mPas) and polyester polyol PF-2011(functionality 2.4, molecular weight 500, viscosity 1000mPas) be placed in vacuum drying oven, 120 ℃ of dry 1.5h, have been dried rear sealed storage.
(2) when polyethers temperature is reduced to room temperature (25 ℃) left and right, take respectively 40 parts (by weight, down together) polyether glycol 303 and 60 parts of polyester polyol PF-2011 are placed in drying receptacle, take successively again 0.5 part of dibutyl tin laurate (DBTDL), the alcoholic solution of 0.5 part of three vinylidene diamines (A33), 2 parts of suds-stabilizing agent silicone oil AK-8805,10 parts of dimethyl methyl phosphonates (DMMP), 200 parts of coumarone-indene resins, with glass stick, stir 40s and be uniformly dispersed to each component, obtain component A.
(3) take 102 parts of polyisocyanates (PAPI), obtain component B.
(4) by component A and component B by volume the ratio mixing and stirring of 3:1 until there is blushing, pour self-vulcanizing in molding jig into, after it solidifies completely, take out sample, place laggard line correlation performance test in three days.
The performance of the urethane slip casting strengthening material that the present embodiment prepares is as follows:
Embodiment 2:
(1) by polyether glycol 4110(functionality 4, molecular weight 500, viscosity 3500 ~ 4500mPas) and polyether glycol 303(functionality 3, molecular weight 350, viscosity 350 ~ 550mPas) be all placed in vacuum drying oven, 120 ℃ of dry 1.5h, answer sealed storage after being dried.
(2) when polyethers temperature is reduced to room temperature (25 ℃) left and right, take respectively 30 parts of polyether glycols 4110 and 70 parts of polyether glycols 303 are placed in drying receptacle, take successively again 1 part of dibutyl tin laurate (DBTDL), the alcoholic solution of 1 part of three vinylidene diamines (A33), 2 parts of suds-stabilizing agent silicone oil AK-8805,10 parts of dimethyl methyl phosphonates (DMMP), 200 parts of coumarone-indene resins, with glass stick, stir 40s and be uniformly dispersed to each component, obtain component A.
(3) take 135 parts of polyisocyanates PAPI, obtain component B.
(4) by component A and component B by volume the ratio mixing and stirring of 3:1 until there is blushing, pour self-vulcanizing in molding jig into, after it solidifies completely, take out sample, place laggard line correlation performance test in three days.
The performance of the urethane slip casting strengthening material that the present embodiment prepares is as follows:
Embodiment 3:
(1) by polyether glycol 4110(functionality 4, molecular weight 500, viscosity 3500 ~ 4500mPas) and aromatic polyester polyol PF-2011(functionality 2.4, molecular weight 500, viscosity 1000mPas) be all placed in vacuum drying oven, 120 ℃ of dry 1.5h, answer sealed storage after being dried.
(2) when polyethers temperature is reduced to room temperature (25 ℃) left and right, take respectively 30 parts of polyether glycols 4110 and 70 parts of aromatic polyester polyol PF-2011 are placed in drying receptacle, take successively again 0.5 part of dibutyl tin laurate (DBTDL), the alcoholic solution of 0.5 part of three vinylidene diamines (A33), 2 parts of suds-stabilizing agent silicone oil AK-8805,7 parts of dimethyl methyl phosphonates, 3 parts of trichloroethyl phosphates, 200 parts of coumarone-indene resins, with glass stick, stir 40s and be uniformly dispersed to each component, obtain reinforcement material component A.
(3) take 93 parts of polyisocyanates PAPI, obtain reinforcement material B component.
(4) by component A and component B by volume the ratio mixing and stirring of 3:1 until there is blushing, pour self-vulcanizing in molding jig into, after it solidifies completely, take out sample, place laggard line correlation performance test in three days.
The performance of the urethane slip casting strengthening material that the present embodiment prepares is as follows:
Embodiment 4:
(1) by polyether glycol 303(functionality 3, molecular weight 350, viscosity 350 ~ 550mPas) and polyether glycol 330(functionality 3, molecular weight 3000, viscosity 500 ~ 700mPas) be all placed in vacuum drying oven, 120 ℃ of dry 1.5h, answer sealed storage after being dried.
(2) when polyethers temperature is reduced to room temperature (25 ℃) left and right, take respectively 70 parts of polyether glycols 303 and 30 parts of polyether glycols 330 are placed in drying receptacle, take successively again 1 part of dibutyl tin laurate (DBTDL), the alcoholic solution of 1 part of three vinylidene diamines (A33), 2 parts of suds-stabilizing agent silicone oil AK-8805,10 parts of DMMP, 150 parts of coumarone-indene resins, with glass stick, stir 40s and be uniformly dispersed to each component, obtain reinforcement material component A.
(3) take 102 parts of polyisocyanates PAPI, obtain reinforcement material B component.
(4) by component A and component B by volume the ratio mixing and stirring of 3:1 until there is blushing, pour self-vulcanizing in molding jig into, after it solidifies completely, take out sample, place laggard line correlation performance test in three days.
The performance of the urethane slip casting strengthening material that the present embodiment prepares is as follows:
Embodiment 5:
(1) by polyether glycol 303(functionality 3, molecular weight 350, viscosity 350 ~ 550mPas) be placed in vacuum drying oven, 120 ℃ of dry 1.5h, answer sealed storage after being dried.
(2) when polyethers temperature is reduced to room temperature (25 ℃) left and right, take 100 parts of polyether glycols 303 and be placed in drying receptacle, take successively again 3 parts of dibutyl tin laurates (DBTDL), the alcoholic solution of 3 part of three vinylidene diamines (A33), 2 parts of suds-stabilizing agent silicone oil AK-8805,10 parts of DMMP, 200 parts of coumarone-indene resins, with glass stick, stir 40s and be uniformly dispersed to each component, obtain reinforcement material component A.
(3) take 138 parts of polyisocyanates PAPI, obtain reinforcement material B component.
(4) by component A and component B by volume the ratio mixing and stirring of 3:1 until there is blushing, pour self-vulcanizing in molding jig into, after it solidifies completely, take out sample, place laggard line correlation performance test in three days.
The performance of the urethane slip casting strengthening material that the present embodiment prepares is as follows:
Claims (8)
1. a low heat release urethane slip casting strengthening material, is characterized in that its raw material is configured to by mass fraction:
100 parts of polymer polyatomic alcohols, amines catalyst 0.5-3.5 part, tin class catalyzer 0.5-3.5 part, suds-stabilizing agent 1-4 part, fire retardant 10-50 part, additive coumarone-indene resin 50-200 part, isocyanic ester 100-200 part;
Described polymer polyatomic alcohol is polyether glycol and/or polyester polyol.
2. low heat release urethane slip casting strengthening material according to claim 1, is characterized in that:
The functionality of described polyether glycol is 2-6, and molecular weight is 100-2000, viscosity 100-1000mPas;
The functionality of described polyester polyol is 2-4, and molecular weight is 200-3000, viscosity 500-2000mPas.
3. low heat release urethane slip casting strengthening material according to claim 1, is characterized in that:
Described isocyanic ester is many methyl polyphenyl polyisocyanate ,-NCO content 30-32%.
4. low heat release urethane slip casting strengthening material according to claim 1, is characterized in that:
Described amines catalyst is selected from N, N '-dimethylcyclohexylamine, three vinylidene diamines, N, N, N', N', N " one or more in five methyl diethylentriamine;
Described tin class catalyzer is selected from stannous octoate or dibutyl tin laurate.
5. low heat release urethane slip casting strengthening material according to claim 1, is characterized in that:
Described suds-stabilizing agent is silicone oil.
6. low heat release urethane slip casting strengthening material according to claim 1, is characterized in that:
Described fire retardant is selected from one or more in ammonium polyphosphate, trichloroethyl phosphate, aluminium hydroxide, dimethyl methyl phosphonate.
7. a preparation method for low heat release urethane slip casting strengthening material claimed in claim 1, comprises and it is characterized in that preparation and each unit process of two fluid grouting of pre-treatment, two components:
Described pre-treatment be by polymer polyatomic alcohol at 110-120 ℃ of vacuum-drying 1-2 hour, be cooled to seal after room temperature standby;
The preparation of described pair of component is that pretreated polymer polyatomic alcohol is mixed, and then adds successively amines catalyst, tin class catalyzer, suds-stabilizing agent, fire retardant and additive coumarone-indene resin, obtains component A after stirring; Isocyanic ester is component B;
Described two fluid grouting is to utilize Double-liquid mud-injection pump component A and B component to be injected to the ground crack needing reinforcement, set time 25-150s.
8. preparation method according to claim 7, is characterized in that:
In two fluid grouting process, coutroi velocity makes component A and component B mix slip casting with the volume ratio of 3:1.
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