CN105670271B - The non-ignitable grade foam gap filler of two component polyurethane, it is prepared and canned gap filler - Google Patents
The non-ignitable grade foam gap filler of two component polyurethane, it is prepared and canned gap filler Download PDFInfo
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- CN105670271B CN105670271B CN201511028110.XA CN201511028110A CN105670271B CN 105670271 B CN105670271 B CN 105670271B CN 201511028110 A CN201511028110 A CN 201511028110A CN 105670271 B CN105670271 B CN 105670271B
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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
- C08L75/06—Polyurethanes from polyesters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D81/00—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents
- B65D81/32—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents for packaging two or more different materials which must be maintained separate prior to use in admixture
- B65D81/3233—Flexible containers disposed within rigid containers
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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
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6648—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6651—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/143—Halogen containing compounds
- C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
-
- 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
- C08G2101/00—Manufacture of cellular products
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/16—Unsaturated hydrocarbons
- C08J2203/162—Halogenated unsaturated hydrocarbons, e.g. H2C=CF2
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/06—Polyurethanes from polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2491/00—Characterised by the use of oils, fats or waxes; Derivatives thereof
- C08J2491/06—Waxes
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/14—Applications used for foams
-
- 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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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Polyurethanes Or Polyureas (AREA)
- Sealing Material Composition (AREA)
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Abstract
The present invention proposes a kind of non-ignitable grade foam gap filler of two component polyurethane, and the ingredient of joint filling is made of component A and B component, and component A consists of the following compositions：100 mass parts of polyester polyol, one fluorine dichloroethanes, 28~32 mass parts, 14~18 mass parts of methyl-phosphoric acid dimethyl ester, three (2 carboxyethyl) phosphines, 20~30 mass parts, 2 mass parts of silicone oil, 1~2 mass parts of catalyst, 0.2~0.4 mass parts of pentamethyl-diethylenetriamine, 70~90 mass parts of potassium silicate, 10~15 mass parts of chlorinated paraffin.Gap filler proposed by the present invention, curing rate is fast after joint filling, and mechanical strength is good；Foamed material for non-ignitable grade.
Description
Technical field
The invention belongs to sealing material fields, and in particular to a kind of gap filler containing polyurethane and its preparation.
Background technology
Cranny filler of polyurethane foam is a kind of one pack system, moisture-curable, multiduty polyurethane foam filling elastic packing
Material.Cranny filler of polyurethane foam is that the components such as polyurethane prepolymer Ti ﹑ Fa Pao Ji ﹑ catalyst are loaded in pressure-resistant inhalator jar
Special polyurethane products.Mist colloid is sprayed to position to be onstructed by mating applicator gun or manual jet pipe during construction, it is short
Phase completes molding, foaming, bonding and seal process.Its cure foam elastomer have bonding, waterproof, it is resistance to expand with heat and contract with cold, be heat-insulated,
The excellent performances such as sound insulation even fire-retardant (limit flame retardant type), are widely used in filling out at building doors and windows side seam, member expansion joint and hole
Fill sealing.
The general surface drying time of cranny filler of polyurethane foam is within 10 minutes (under 20 DEG C of environment of room temperature), and the absolutely dry time is with ring
Border temperature and humidity and it is different, under normal circumstances, summer is absolutely dry about 4-6 hours time, and winter zero degree or so then needs 24
Hour or longer time could be absolutely dry.(and in the case where its appearance has coating) in normal conditions of use, estimates its clothes
The service life be engaged in not less than 10 years, cures foams within the temperature range of -10 DEG C~80 DEG C and keeps good elasticity and cohesive force.
Since beginning of this century last century Mo, this product promoted and applied at home, market demand expands rapidly, at present
The annual consumption of national construction market is about in 30,000,000 tanks or so, raising and energy-saving type building with construction quality requirement
Popularization, the dosage of such product is from now on also by steady-state growth.
At present, the conventional formulation of the type product is generally using the floride-free foaming agent for not destroying ozone layer.But it is filled out in tank body
The propellant filled often brings the risk of explosion.The formula of gap filler and canned structure are improved, it is dangerous that its can be solved
Factor.
Invention content
In view of the deficiencies of the prior art, the purpose of the present invention is to propose to a kind of non-ignitable grade foams of two component polyurethane to fill out
Stitch agent.
It is another object of the present invention to propose a kind of canned gap filler.
Realize the object of the invention technical solution be：
A kind of non-ignitable grade foam gap filler of two component polyurethane, the ingredient of joint filling are made of component A and B component,
The component A consists of the following compositions：100 mass parts of polyester polyol, 28~32 mass parts of a fluorine dichloroethanes,
14~18 mass parts of methyl-phosphoric acid dimethyl ester (DMMP), three (2- carboxyethyls) phosphine (TCEP) 20~30 mass parts, 2 mass of silicone oil
Part, 1~2 mass parts of catalyst, 0.2~0.4 mass parts of pentamethyl-diethylenetriamine, 70~90 mass parts of potassium silicate, chlorination stone
10~15 mass parts of wax；
The B component is isocyanates.
Gap filler proposed by the present invention, main component is polyester polyol in component A, and DMMP and TCEP are fire retardant.
Preferably, polyester polyol is the polyester polyol that hydroxyl value is 200-400mg KOH/g.
For the solid content of the potassium silicate more than 98%, the chlorinity of the chlorinated paraffin is 50~70%.
Using a large amount of potassium silicates in gap filler proposed by the present invention, potassium silicate is commonly called as potash glass, solid content 98% with
On potassium silicate room temperature under for liquid, mixing dispersion effect is good, is expanded when meeting fire, forms hard shell, realize fire-retardant effect.Chlorine
Fossil waxes have lubricating action, and the fireproofing function that chlorinity is 50~70% is preferable.More preferably chlorinated paraffin -52.
Wherein, the catalyst is catalyst PC-41 and catalyst DMP-30, and the mass ratio of the two is 0.5~0.7：1.
Above two one is kicker, and one is curing catalysts, and two kinds are used in combination, and expansion rate is fast.Only
It will appear bubble phenomenon of collapsing using catalyst DMP-30.
It is highly preferred that the B component is isocyanates PM-200.
Wherein, the preparation method of the component A is：In room temperature environment, polyester polyol, a fluorine dichloroethanes, DMMP,
TCEP, silicone oil, catalyst PC-41, catalyst DMP-30, pentamethyl-diethylenetriamine mixing, high-speed stirred add after 1~2 minute
Enter potassium silicate and chlorination stone, then high-speed stirred 20~40 minutes；The rotating speed of the high-speed stirred is 1000-1500 revs/min.
A kind of canned gap filler is the non-ignitable grade foam joint filling of the two component polyurethane of the present invention contained in metal can
Agent；Component A is placed in A capsules, and B component is placed in B capsules, the outlet connection outlet pipeline of A capsules and B capsules, outlet conduit
Upper setting push type valve, the end of outlet conduit is nozzle；It is equipped in region in metal can tank skin, outside A capsules and B capsules
Third butane.
Wherein, A capsules and B capsules are same material, are in nitrile rubber, organic silicon rubber and polyurethane elastomer
One kind is raw material, and die pressing is made.
Further, the outlet aperture of A capsules is 1mm, and the outlet aperture of B capsules is 1.8mm, is set in the outlet conduit
It is equipped with static mixer.
The static mixer is the device for setting mixing component in the duct, opens that there are two import, two groups on pipeline
It respectively enters, is stirred in pipeline, sprayed by nozzle.In the present invention, the outlet of A capsules is that component A enters
The import of static mixer, aperture 1mm, the outlet as B component of B capsules enter the import of static mixer, aperture
For 1.8mm.
Preferably, metal tank volume, A capsules volume, B capsules volume, the third butane volume ratio be 900：180~220：
5:3~280：120~150.
The beneficial effects of the present invention are：
Gap filler proposed by the present invention, curing rate is fast after joint filling, and mechanical strength is good；Foamed material for non-ignitable grade；
Canned gap filler proposed by the present invention, overcome be separately provided propellant cause cranny filler of polyurethane foam it is inflammable,
Explosive problem；It is attached separately in two capsules of tank body to make material propellant with the third butane with two component polyurethane and causes double groups
Divide material extrusion mixing, achieve the purpose that foaming.
Description of the drawings
Fig. 1 is canned gap filler structure chart proposed by the present invention；
Fig. 2 is Fig. 1 push type valve mechanism schematic diagrames.
In figure, 1 is static mixer, and 2 be A capsules, and 3 be B capsules, and 4 be metal can, and 5 be nozzle, and 6 be push type valve.
Specific embodiment
The present invention is now illustrated, but be not limited to the scope of the present invention with following embodiment.The hand used in embodiment
Section, unless otherwise instructed, using the means of this field routine.
Below in conjunction with the attached drawing in the embodiment of the present invention, the technical solution in the embodiment of the present invention is carried out clear, complete
Site preparation describes, it is clear that described embodiment is only part of the embodiment of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, those of ordinary skill in the art are obtained every other without creative efforts
Embodiment shall fall within the protection scope of the present invention.
Embodiment 1：The non-ignitable grade foam gap filler of two component polyurethane
Gap filler is made of component A and B component, the preparation of component A：In 20 DEG C of environment of room temperature, polyester polyol is taken
SKR-240B (Si Kerui polyurethane materials Co., Ltd produces, hydroxyl value 240 ± 10) 100 mass parts, 30 mass of a fluorine dichloroethanes
Part, 15 mass parts of DMMP, 25 mass parts of TCEP, 2 mass parts of silicone oil, 0.6 mass parts of catalyst PC-41, catalyst DMP-30
0.9 mass parts, the mixing of 0.3 mass parts of pentamethyl-diethylenetriamine, 1500 revs/min of high-speed stirreds add silicic acid after 1 minute
Potassium (more than 98% solid content) 80 mass parts, 13 mass parts of chlorinated paraffin -52, high-speed stirred 30 minutes.
B component：Isocyanates PM-200.
Embodiment 2：Canned gap filler
The tank structure used is shown in Fig. 1.
1 gap filler processed of embodiment is contained in 900mL metal cans 4 (aluminium alloy can), component A is placed in A capsules 2, B component
It is placed in B capsules 3, the outlet connection outlet pipeline of A capsules and B capsules, push type valve 6 is provided on outlet conduit；Metal
In tank tank skin, the third butane of 130mL is housed outside A capsules and B capsules.
See Fig. 2, fill out the outlet in A capsule outlets and B capsules in push type valve 6 respectively there are two sphere.By lower valve
Component A and B component can then be sprayed simultaneously (the third butane does not gush out, and plays a part of to squeeze capsule).
A capsules and B capsules are soft capsule, are made with nitrile rubber die pressing.
Wherein, the outlet aperture of A capsules is 1mm, and the outlet aperture of B capsules is 1.8mm, is connected to static mixer
1 two imports, the port of export setting nozzle 5 of static mixer 1.Agitating element is provided in the pipeline of static mixer 1, when
Propellant can automatic stirring when being pushed into.Propellant is the third butane.
By 208 grams of component A material loading A capsules, 343 grams of loading B capsules of B component, under the operation temperature below 20 DEG C,
Third butane is packed into metal can (the third butane below 20 DEG C of temperature is liquid), A, B capsule are then packed into tank body, then installation outlet
Pipeline.Up to canned gap filler.
Embodiment 3
Gap filler made from embodiment 2 is sprayed at cement matrix surface, blisters within 3 seconds, becomes larger rapidly at once, and 10 minutes solid
Change, reach work hardness after 4 hours, you can be tested for the property.Gap filler is sprayed at wood surface and surface of metal product,
The performance of joint filling after test is dry respectively.
Mechanics Performance Testing：It is 0.1MP with cement products surface adhesive strength, is with surface of metal product adhesive strength
0.08MP is 0.096MP with wood surface adhesive strength.As a result superior or equal to existing products in markets.
Combustibility is tested：With butane blowtorch burning material 20 minutes.Without combustion phenomena.
Material characteristics：5 DEG C -45 DEG C can normal use.Hardening time is 20 minutes.
Above embodiment be only the preferred embodiment of the present invention is described, not to the scope of the present invention into
Row limits, and under the premise of design spirit of the present invention is not departed from, this field ordinary skill technical staff is to the technical side of the present invention
The all variations and modifications that case is made should all be fallen into the protection domain that claims of the present invention determines.
Claims (2)
1. a kind of canned gap filler, which is characterized in that the non-ignitable grade foam gap filler of two component polyurethane, institute are contained in metal can
The ingredient for stating the non-ignitable grade foam gap filler of two component polyurethane is made of component A and B component,
The component A consists of the following compositions：100 mass parts of polyester polyol, 28 ~ 32 mass parts of a fluorine dichloroethanes, methyl
14 ~ 18 mass parts of dimethyl phosphate, three (2- carboxyethyls) phosphines, 20 ~ 30 mass parts, 2 mass parts of silicone oil, 1 ~ 2 mass parts of catalyst,
0.2 ~ 0.4 mass parts of pentamethyl-diethylenetriamine, 70 ~ 90 mass parts of potassium silicate, 10 ~ 15 mass parts of chlorinated paraffin -52；
The B component is isocyanates PM-200；
Wherein, in the component A, polyester polyol is the polyester polyol that hydroxyl value is 200 ~ 400mgKOH/g, the potassium silicate
Solid content more than 98%, the chlorinity of the chlorinated paraffin is 50 ~ 70%；The catalyst is catalyst PC-41 and urges
Agent DMP-30, the mass ratio of the two is 0.5 ~ 0.7：1 ；
The preparation method of the component A is：In room temperature environment, polyester polyol, a fluorine dichloroethanes, DMMP, TCEP, silicon
Oil, the mixing of catalyst PC-41, catalyst DMP-30, pentamethyl-diethylenetriamine, high-speed stirred add in silicic acid after 1 ~ 2 minute
Potassium and chlorinated paraffin, then high-speed stirred 20 ~ 40 minutes；The rotating speed of the high-speed stirred is 1000 ~ 1500 revs/min；
Component A is placed in A capsules, and B component is placed in B capsules, the outlet connection outlet pipeline of A capsules and B capsules, outlet conduit
Upper setting push type valve, the end of outlet conduit is nozzle；In metal can tank skin, the third butane is housed outside A capsules and B capsules；A
The outlet aperture of capsule is 1mm, and the outlet aperture of B capsules is 1.8mm, and static mixer is provided in the outlet conduit.
2. canned gap filler according to claim 1, which is characterized in that A capsules and B capsules are same material, be with
A kind of in nitrile rubber, organic silicon rubber and polyurethane elastomer is raw material, and die pressing is made.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201511028110.XA CN105670271B (en) | 2015-12-31 | 2015-12-31 | The non-ignitable grade foam gap filler of two component polyurethane, it is prepared and canned gap filler |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201511028110.XA CN105670271B (en) | 2015-12-31 | 2015-12-31 | The non-ignitable grade foam gap filler of two component polyurethane, it is prepared and canned gap filler |
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| CN105670271A CN105670271A (en) | 2016-06-15 |
| CN105670271B true CN105670271B (en) | 2018-07-10 |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108865042A (en) * | 2017-05-15 | 2018-11-23 | 山东居欢新型材料科技有限公司 | A kind of B1 grades of flame retardant type single-component cranny filler of polyurethane foam and preparation method thereof |
| CN114573778A (en) * | 2022-03-04 | 2022-06-03 | 固诺（天津）实业有限公司 | Low-pressure bi-component foamed polyurethane and application thereof |
| CN114572563B (en) * | 2022-03-04 | 2024-03-12 | 固诺（天津）实业有限公司 | Double-component adhesive packaging bag, double-component foaming polyurethane and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN201823647U (en) * | 2010-09-30 | 2011-05-11 | 孙光辉 | Novel fast and airtight spraying device |
| CN103408721A (en) * | 2013-08-26 | 2013-11-27 | 大同煤矿集团有限责任公司 | High polymer chemistry coal and rock mass reinforcer for coal mines |
| CN103724581A (en) * | 2013-12-30 | 2014-04-16 | 辽宁工程技术大学 | Polyurethane gas hole sealing material for underground coal mine and preparation method thereof |
| CN103819649A (en) * | 2012-11-19 | 2014-05-28 | 廊坊开发区斯科瑞聚氨酯有限公司 | Production method for portable self-spraying bi-component foam caulking agent |
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2015
- 2015-12-31 CN CN201511028110.XA patent/CN105670271B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN201823647U (en) * | 2010-09-30 | 2011-05-11 | 孙光辉 | Novel fast and airtight spraying device |
| CN103819649A (en) * | 2012-11-19 | 2014-05-28 | 廊坊开发区斯科瑞聚氨酯有限公司 | Production method for portable self-spraying bi-component foam caulking agent |
| CN103408721A (en) * | 2013-08-26 | 2013-11-27 | 大同煤矿集团有限责任公司 | High polymer chemistry coal and rock mass reinforcer for coal mines |
| CN103724581A (en) * | 2013-12-30 | 2014-04-16 | 辽宁工程技术大学 | Polyurethane gas hole sealing material for underground coal mine and preparation method thereof |
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