CN109372548B - Hyperbranched polymer tackifying dust-free guniting material for underground coal mine roadway - Google Patents
Hyperbranched polymer tackifying dust-free guniting material for underground coal mine roadway Download PDFInfo
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- CN109372548B CN109372548B CN201811336479.0A CN201811336479A CN109372548B CN 109372548 B CN109372548 B CN 109372548B CN 201811336479 A CN201811336479 A CN 201811336479A CN 109372548 B CN109372548 B CN 109372548B
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- hyperbranched polymer
- coal mine
- guniting
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Classifications
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- E—FIXED CONSTRUCTIONS
- E21—EARTH DRILLING; MINING
- E21D—SHAFTS; TUNNELS; GALLERIES; LARGE UNDERGROUND CHAMBERS
- E21D11/00—Lining tunnels, galleries or other underground cavities, e.g. large underground chambers; Linings therefor; Making such linings in situ, e.g. by assembling
- E21D11/04—Lining with building materials
- E21D11/10—Lining with building materials with concrete cast in situ; Shuttering also lost shutterings, e.g. made of blocks, of metal plates or other equipment adapted therefor
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH DRILLING; MINING
- E21D—SHAFTS; TUNNELS; GALLERIES; LARGE UNDERGROUND CHAMBERS
- E21D11/00—Lining tunnels, galleries or other underground cavities, e.g. large underground chambers; Linings therefor; Making such linings in situ, e.g. by assembling
- E21D11/38—Waterproofing; Heat insulating; Soundproofing; Electric insulating
Abstract
The invention relates to the field of coal mine underground roadway dust-free guniting materials, in particular to a hyperbranched polymer tackifying coal mine underground roadway dust-free guniting material. Firstly, a hydroxyl-terminated hyperbranched polymer is synthesized, then double bonds are introduced into the tail end of the hyperbranched polymer through acrylic acid modification, and then the hyperbranched polymer is polymerized with vinyl acetate emulsion, so that the hyperbranched polymer for the dust-free guniting material for the underground roadway of the thickening coal mine is synthesized. The hyperbranched polymer is applied to the field of dust-free guniting materials for underground roadways of coal mines, has good tackifying, waterproof and anti-cracking effects, reduces raw material waste, reduces cost, and is good in stability, lasting in effect and convenient to construct.
Description
Technical Field
The invention relates to the technical field of coal mine underground roadway dust-free guniting materials, in particular to a hyperbranched polymer tackifying coal mine underground roadway dust-free guniting material.
Background
In recent years, global economy has continued to increase, and the prices of oil and gas have risen dramatically, resulting in a rapid increase in global coal demand. Coal is the most abundant (about 90% of the total reserves of various energy sources), the most widely distributed and the cheapest energy source in the world. Along with the rapid development of industries such as electric power, metallurgy, building materials, chemical engineering and the like in China, the demand for coal is greatly increased. According to the economic and recoverable reserves of hard coal, the reserves of Chinese coal account for 11 percent of the total reserves of coal in the world, and rank the third in the world, but the reserves of the coal suitable for open-pit mining in China are few, and the coal is generally mined and transported underground.
In order to protect the underground coal mine roadway, the traditional method is to carry out concrete guniting support, namely cement, gravel and other auxiliaries in a certain proportion are uniformly stirred on site, the concrete guniting support is put into a guniting machine, the guniting machine is mixed with water at a gun nozzle of the guniting machine in a wind power transportation mode, the mixture is sprayed to the surface of a mined rock stratum, the rock stratum is subjected to closed protection after being solidified, effective effects such as rock collapse prevention can be achieved, and the traditional stirring mode and guniting materials have many defects: firstly, cement gravel is mixed in a dry method on site, dust generated by wind power transmission is seriously polluted, and great threat is caused to the health of construction workers in the past for a long time; secondly, the traditional guniting material has poor adhesion performance and large resilience, so that part of guniting material falls on the ground, a large amount of guniting material is needed to protect the surface of a rock stratum, and serious waste is caused; most of the components of the re-guniting material are rigid components, and the re-guniting material is high in brittleness, so that the traditional guniting material is easy to crack, and the consequences of water seepage, local collapse and the like are caused.
The invention aims to add a novel high-efficiency high-viscosity hyperbranched polymer emulsion as a modified material of a traditional coal mine underground roadway guniting material. The hyperbranched polymer has a three-dimensional network structure, a plurality of active sites, low viscosity, good fusion with a matrix and wide application prospect, and shows great application value in the fields of photoelectric materials, coatings, adhesives, nanotechnology, drug delivery and the like. The hyperbranched polymer emulsion synthesized by taking the hyperbranched polymer as a monomer has a large number of polar functional groups, so that the adhesive force of the hyperbranched polymer emulsion to rock strata is enhanced, the traditional guniting material has stronger adhesion and elasticity, and the problems of guniting material waste and dust pollution are solved. In addition, the hyperbranched emulsion is water-soluble, is suitable for being mixed with cement, and has good compatibility.
Disclosure of Invention
The invention provides a hyperbranched polymer for an enhanced-viscosity coal mine underground roadway dustless guniting material, aiming at solving the problem of poor adhesion performance of the traditional coal mine underground roadway guniting material.
The invention also provides a preparation method of the hyperbranched polymer.
The invention is realized by the following measures:
a hyperbranched polymer-thickened coal mine underground roadway dustless guniting material is characterized in that the hyperbranched polymer is hyperbranched VAE (vinyl acetate-ethylene) emulsion obtained by polymerizing double-bond-terminated hyperbranched polymer and vinyl acetate.
The hyperbranched VAE emulsion is obtained by the following steps:
(1)AB2synthesis of monomers
Equimolar amounts of maleic anhydride and diethanolamine were reacted as follows:
(2) synthesis of core molecules trimethylolpropane and AB of hydroxyl-terminated hyperbranched polymer2The monomers were reacted as follows:
(3) synthesis of double-bond-terminated hyperbranched polymer
The hydroxyl-terminated hyperbranched polymer reacts with acrylic acid, and the synthesized double-bond-terminated hyperbranched polymer has the following structure:
(4) the synthesis of the hyperbranched polymer with double bond at the end of the hyperbranched VAE emulsion and the polymerization of the vinyl acetate emulsion are carried out as follows:
wherein, the middle circle represents the hydroxyl-terminated hyperbranched polymer which is synthesized in the step (2) and is removed from the hydroxyl groups, and the obtained product is the hyperbranched polymer with double bonds at the end group and the hyperbranched VAE emulsion obtained by polymerizing the vinyl acetate emulsion.
The hyperbranched polymer of the tackifying coal mine underground roadway dustless guniting material comprises first generation nuclear molecules, second generation nuclear molecules, third generation nuclear molecules and fourth generation nuclear molecules and AB2The molar ratio of the monomers is 1: 3. 1: 9. 1: 21. 1: 45.
the molar ratio of the first generation nuclear molecule, the second generation nuclear molecule, the third generation nuclear molecule and the fourth generation nuclear molecule to the acrylic acid of the hyperbranched polymer of the tackifying coal mine underground roadway dustless guniting material is 1: 6. 1: 12. 1: 24. 1: 48.
the hyperbranched polymer of the dust-free guniting material for the underground roadway of the tackifying coal mine is prepared by polymerizing a hyperbranched polymer with double bonds at the end group and vinyl acetate through emulsion, wherein the molar ratio of the hyperbranched polymer to the vinyl acetate is 1: 6. 1: 12. 1: 24. 1: 48.
the problems of material waste, cost increase, potential safety hazard and the like are caused by poor adhesion of the guniting material and the surface of the rock stratum of the underground roadway of the coal mine. Therefore, the hyperbranched polymer containing a large number of active groups is introduced, so that the traditional guniting material has certain elasticity, and the phenomena of rock stratum collapse and cracking can be reduced. According to the invention, the hyperbranched emulsion with excellent performance is synthesized through emulsion polymerization, so that the guniting material has a large number of polar groups and has strong adhesive property with the surface of a rock stratum, and the dosage of the guniting material is further reduced. In addition, when the hyperbranched emulsion is mixed with a guniting material, a compact high-molecular film-shaped substance is formed in cement, so that the waterproof effect is achieved.
The invention has the beneficial effects that:
the hyperbranched polymer used as the dust-free guniting material for the underground roadway of the tackifying coal mine can obviously improve the bonding performance of the guniting material and the surface of the rock stratum of the underground roadway of the coal mine, reduce the waste of raw materials and reduce the cost; meanwhile, the prepared guniting material has stronger waterproofness, is a hyperbranched polymer which is used as a dustless guniting material for the underground roadway of the tackifying coal mine, has good stability, lasting effect and simple synthesis process, is convenient for industrial production, and has good market development prospect.
Detailed Description
The following is a more detailed description of the embodiments of the present invention, which is intended to illustrate the concepts and features of the invention, and not to limit the scope of the invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Implementation method one
(1) BalanceFirstly, taking 44.127g (0.45 mol) of maleic anhydride and 47.313g (0.45 mol) of diethanolamine, adding the diethanolamine into a three-neck flask with a magnetic stirrer, and dissolving succinic anhydride with a proper amount of DMAc; then slowly dripping the mixture into a three-necked bottle filled with diethanol amine while stirring, finishing dripping within 1-2 h, and reacting at normal temperature for 8-9 h to obtain the reaction product AB2A type monomer. Adding 120 mL of toluene (toluene is used as a water-carrying agent) into the system, then adding 20.127g (0.15 mol) of trimethylolpropane as a nuclear molecule, and adding 0.500g of p-toluenesulfonic acid as a catalyst; heating was then started until boiling and reflux in the bulb was generated. And keeping the temperature for reaction for 9-10 h to obtain the hyperbranched polymer solution with the terminal being hydroxyl.
(2) And (2) carrying out rotary evaporation on the obtained solution to obtain a light yellow viscous hyperbranched polymer, weighing 5.000g (0.90 mol) of hydroxyl-terminated hyperbranched polymer, putting the light yellow viscous hyperbranched polymer into a three-mouth bottle, adding 30ml of DMAc to dissolve the DMAc, slowly dropwise adding 8ml of acrylic acid into the three-mouth bottle, completing dropwise adding for 0.5-1h, adding 0.070g of p-toluenesulfonic acid as a catalyst and 0.200g of hydroquinone polymerization inhibitor, and then reacting for 6-7h at 135-140 ℃ to obtain the hyperbranched polymer with double bonds at the tail end, namely the monomer used by the hyperbranched polymer emulsion.
(3) Dissolving 1.2g of emulsifier SDS and 100.4 g of emulsifier OP in 85g of deionized water, then adding 81g of monomer vinyl acetate, uniformly stirring, and stirring for 30min to obtain a pre-emulsion; adding the rest of emulsifier and deionized water into a four-mouth bottle provided with a mechanical stirrer, a condenser tube and a thermometer, heating to 75 ℃, adding 1g of ammonium persulfate initiator solution, gradually dropwise adding 1g of double-bond terminated hyperbranched polymer, controlling the pressure to be 4MPa, reacting for 3 hours at 78 ℃, adding ammonia water to neutralize the emulsion until the pH value is 7-8, and bottling and storing to obtain the hyperbranched VAE emulsion.
Implementation method two
(1) 44.127g (0.45 mol) of maleic anhydride and 47.313g (0.45 mol) of diethanolamine are weighed, firstly, the diethanolamine is added into a three-neck flask with a magnetic stirrer, and then succinic anhydride is dissolved by a proper amount of DMAc; then slowly adding the mixture into a three-neck bottle filled with diethanol amine while drippingStirring while dripping, finishing dripping for 1-2 h, and reacting at normal temperature for 8-9 h to obtain AB2A type monomer. Adding 120 mL of toluene (toluene is used as a water-carrying agent) into the system, then adding 20.127g (0.15 mol) of trimethylolpropane as a nuclear molecule, and adding 0.500g of p-toluenesulfonic acid as a catalyst; heating was then started until boiling and reflux in the bulb was generated. And keeping the temperature for reaction for 9-10 h to obtain the hyperbranched polymer solution with the terminal being hydroxyl.
(2) And (2) carrying out rotary evaporation on the obtained solution to obtain a light yellow viscous hyperbranched polymer, weighing 5.000g (0.90 mol) of hydroxyl-terminated hyperbranched polymer, putting the light yellow viscous hyperbranched polymer into a three-necked bottle, adding 30ml of DMAc to dissolve the DMAc, slowly dropwise adding 10ml of acrylic acid into the three-necked bottle, completing dropwise adding for 0.5-1h, adding 0.080g of p-toluenesulfonic acid as a catalyst and 0.200g of hydroquinone polymerization inhibitor, and then reacting for 6-7h at 135-140 ℃ to obtain a hyperbranched polymer with double bonds at the tail end, namely the monomer used by the hyperbranched polymer emulsion.
(3) Dissolving 1.2g of emulsifier SDS and 100.4 g of emulsifier OP in 85g of deionized water, then adding 81g of monomer vinyl acetate, uniformly stirring, and stirring for 30min to obtain a pre-emulsion; adding the rest of emulsifier and deionized water into a four-mouth bottle provided with a mechanical stirrer, a condenser tube and a thermometer, heating to 75 ℃, adding 1g of ammonium persulfate initiator solution, gradually dropwise adding 1g of double-bond terminated hyperbranched polymer, controlling the pressure to be 4MPa, reacting for 3 hours at 78 ℃, adding ammonia water to neutralize the emulsion until the pH value is 7-8, and bottling and storing to obtain the hyperbranched VAE emulsion.
Implementation method three
(1) 44.127g (0.45 mol) of maleic anhydride and 47.313g (0.45 mol) of diethanolamine are weighed, firstly, the diethanolamine is added into a three-neck flask with a magnetic stirrer, and then succinic anhydride is dissolved by a proper amount of DMAc; then slowly dripping the mixture into a three-necked bottle filled with diethanol amine while stirring, finishing dripping within 1-2 h, and reacting at normal temperature for 8-9 h to obtain the reaction product AB2A type monomer. 120 mL of toluene (toluene as a water-carrying agent) was added to the system, 20.127g (0.15 mol) of trimethylolpropane was added as a core molecule, and 0 was added.500g of p-toluenesulfonic acid was used as a catalyst; heating was then started until boiling and reflux in the bulb was generated. And keeping the temperature for reaction for 9-10 h to obtain the hyperbranched polymer solution with the terminal being hydroxyl.
(2) And (2) carrying out rotary evaporation on the obtained solution to obtain a light yellow viscous hyperbranched polymer, weighing 5.000g (0.90 mol) of hydroxyl-terminated hyperbranched polymer, putting the light yellow viscous hyperbranched polymer into a three-neck flask, adding 30ml of DMAc to dissolve the DMAc, slowly dropwise adding 12ml of acrylic acid into the three-neck flask, completing dropwise adding for 0.5-1h, adding 0.090g of p-toluenesulfonic acid as a catalyst and 0.200g of hydroquinone polymerization inhibitor, and then reacting for 6-7h at 135-140 ℃ to obtain the hyperbranched polymer with double bonds at the tail end, namely the monomer used by the hyperbranched polymer emulsion.
(3) Dissolving 1.2g of emulsifier SDS and 100.4 g of emulsifier OP in 85g of deionized water, then adding 81g of monomer vinyl acetate, uniformly stirring, and stirring for 30min to obtain a pre-emulsion; adding the rest of emulsifier and deionized water into a four-mouth bottle provided with a mechanical stirrer, a condenser tube and a thermometer, heating to 75 ℃, adding 1g of ammonium persulfate initiator solution, gradually dropwise adding 1g of double-bond terminated hyperbranched polymer, controlling the pressure to be 4MPa, reacting for 3 hours at 78 ℃, adding ammonia water to neutralize the emulsion until the pH value is 7-8, and bottling and storing to obtain the hyperbranched VAE emulsion.
Implementation method four
(1) 44.127g (0.45 mol) of maleic anhydride and 47.313g (0.45 mol) of diethanolamine are weighed, firstly, the diethanolamine is added into a three-neck flask with a magnetic stirrer, and then succinic anhydride is dissolved by a proper amount of DMAc; then slowly dripping the mixture into a three-necked bottle filled with diethanol amine while stirring, finishing dripping within 1-2 h, and reacting at normal temperature for 8-9 h to obtain the reaction product AB2A type monomer. Adding 120 mL of toluene (toluene is used as a water-carrying agent) into the system, then adding 20.127g (0.15 mol) of trimethylolpropane as a nuclear molecule, and adding 0.500g of p-toluenesulfonic acid as a catalyst; heating was then started until boiling and reflux in the bulb was generated. And keeping the temperature for reaction for 9-10 h to obtain the hyperbranched polymer solution with the terminal being hydroxyl.
(2) And (2) carrying out rotary evaporation on the obtained solution to obtain a light yellow viscous hyperbranched polymer, weighing 5.000g (0.90 mol) of hydroxyl-terminated hyperbranched polymer, putting the light yellow viscous hyperbranched polymer into a three-neck flask, adding 30ml of DMAc to dissolve the DMAc, slowly dropwise adding 14ml of acrylic acid into the three-neck flask, completing dropwise adding for 0.5-1h, adding 0.100g of p-toluenesulfonic acid as a catalyst and 0.200g of hydroquinone polymerization inhibitor, and then reacting for 6-7h at 135-140 ℃ to obtain a hyperbranched polymer with double bonds at the tail end, namely the monomer used by the hyperbranched polymer emulsion.
(3) Dissolving 1.2g of emulsifier SDS and 100.4 g of emulsifier OP in 85g of deionized water, then adding 81g of monomer vinyl acetate, uniformly stirring, and stirring for 30min to obtain a pre-emulsion; adding the rest of emulsifier and deionized water into a four-mouth bottle provided with a mechanical stirrer, a condenser tube and a thermometer, heating to 75 ℃, adding 1g of ammonium persulfate initiator solution, gradually dropwise adding 1g of double-bond terminated hyperbranched polymer, controlling the pressure to be 4MPa, reacting for 3 hours at 78 ℃, adding ammonia water to neutralize the emulsion until the pH value is 7-8, and bottling and storing to obtain the hyperbranched VAE emulsion.
Performance testing
In order to illustrate the practical effect of the invention, the hyperbranched polymer obtained in the implementation method of the invention with different proportions is added when the quantitatively packaged (25 kg/bag) coal mine underworkings guniting material and a certain proportion of water are mixed in a novel screw type wet guniting machine, and the effect is tested and evaluated.
In the test, taking hyperbranched VAE emulsion obtained by emulsion polymerization of a second-generation double-bond terminated hyperbranched polymer and vinyl acetate as monomers as an example, wet mortar is sprayed on the surface of rock by wind power through a mortar spraying pipeline for testing, and the test performances are respectively shown in the following table 1.
Table 1 effectiveness test of guniting materials
As can be seen from Table 1, the prepared coal mine underground roadway dust-free guniting material has greatly improved bonding property compared with the traditional guniting material after the hyperbranched polymer prepared by the invention is doped.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the embodiments, and any other changes, modifications, combinations, substitutions and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents and are included in the scope of the present invention.
Claims (1)
1. A hyperbranched polymer-thickened coal mine underground roadway dustless guniting material is characterized in that the hyperbranched polymer is hyperbranched vinyl acetate-ethylene emulsion obtained by polymerizing double-bond-terminated hyperbranched polymer and vinyl acetate, and the hyperbranched vinyl acetate-ethylene emulsion is obtained by the following steps:
(1)AB2synthesis of monomers
Equimolar amounts of maleic anhydride and diethanolamine were reacted as follows:
(2) synthesis of hydroxyl-terminated hyperbranched polymer
Core molecules trimethylolpropane and AB2The monomers were reacted as follows:
(3) synthesis of double-bond-terminated hyperbranched polymer
The hydroxyl-terminated hyperbranched polymer reacts with acrylic acid, and the synthesized double-bond-terminated hyperbranched polymer has the following structure:
(4) synthesis of hyperbranched vinyl acetate-ethylene emulsion
Polymerizing a double-bond-terminated hyperbranched polymer and vinyl acetate emulsion, wherein the reaction is as follows:
wherein, the middle circle represents the hydroxyl-terminated hyperbranched polymer which is synthesized in the step (2) and is removed of the hydroxyl; the hyperbranched polymer is used as a tackifier of a coal mine underground roadway dust-free guniting material, and the addition amount of the hyperbranched polymer is 3-9% of that of the coal mine underground roadway guniting material.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101381457A (en) * | 2007-09-05 | 2009-03-11 | 中国科学院成都有机化学有限公司 | Preparation method of aqueous hyperbranched intermediate and water soluble hyperbranched propenoic acid resin |
| CN107010903A (en) * | 2017-05-16 | 2017-08-04 | 巴东 | Exempt from basal plane processing and the sprayable anti-hollowing motar of cracking resistance and its construction method |
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| WO2017049319A1 (en) * | 2015-09-18 | 2017-03-23 | California Institute Of Technology | Associative polymers for use in a flow and related compositions, methods and systems |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101381457A (en) * | 2007-09-05 | 2009-03-11 | 中国科学院成都有机化学有限公司 | Preparation method of aqueous hyperbranched intermediate and water soluble hyperbranched propenoic acid resin |
| CN107010903A (en) * | 2017-05-16 | 2017-08-04 | 巴东 | Exempt from basal plane processing and the sprayable anti-hollowing motar of cracking resistance and its construction method |
Non-Patent Citations (2)
| Title |
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| 无尘高粘干混喷浆材料的研究与应用无尘高粘干混喷浆材料的研究与应用;寿崇琦等;《混凝土》;20071231(第208期);1 * |
| 超支化聚（酰胺一酯）的合成与端基改性;张娜等;《热固性树脂》;20050531;第20卷(第3期);3-4 * |
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