CN117624872A - Novel mining composite material supporting belt and preparation process thereof - Google Patents
Novel mining composite material supporting belt and preparation process thereof Download PDFInfo
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- CN117624872A CN117624872A CN202311496209.7A CN202311496209A CN117624872A CN 117624872 A CN117624872 A CN 117624872A CN 202311496209 A CN202311496209 A CN 202311496209A CN 117624872 A CN117624872 A CN 117624872A
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- 239000003063 flame retardant Substances 0.000 claims abstract description 31
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- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000003292 glue Substances 0.000 claims description 12
- 238000002347 injection Methods 0.000 claims description 12
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- BZQKBFHEWDPQHD-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-[2-(2,3,4,5,6-pentabromophenyl)ethyl]benzene Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1CCC1=C(Br)C(Br)=C(Br)C(Br)=C1Br BZQKBFHEWDPQHD-UHFFFAOYSA-N 0.000 claims description 7
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 7
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 7
- 229920000570 polyether Polymers 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 239000002270 dispersing agent Substances 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 238000005086 pumping Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical class OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 239000000835 fiber Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims description 4
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- 239000000203 mixture Substances 0.000 claims description 4
- 238000000643 oven drying Methods 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
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- 238000003860 storage Methods 0.000 claims description 4
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical class [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- 239000002518 antifoaming agent Substances 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
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- 239000002245 particle Substances 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 3
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- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical class O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 2
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- 239000006082 mold release agent Substances 0.000 claims description 2
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Landscapes
- Reinforced Plastic Materials (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention relates to the technical field of roadway support materials, and particularly discloses a novel mining composite support belt and a preparation process thereof. This novel mining composite material support area, its characterized in that: the polyurethane is prepared from polyurethane, a flame retardant, oxidized carbon black and glass fiber fabric through a pultrusion process, wherein the polyurethane is prepared by mixing a polyol combination material and isocyanate, and the weight percentages of the raw materials are as follows: 5-10% of polyol combination material, 6-16% of isocyanate, 0.3-1% of flame retardant, 0.2-3% of oxidized carbon black and 70-88.5% of glass fiber fabric. The invention is characterized in that the polyol mixture and isocyanate are injected into a mould according to a proportion, mixed and infiltrated with glass fiber in a mould cavity, and formed into the glass fiber reinforced polyurethane composite material through high-temperature solidification and pultrusion, and finally the composite material support belt obtained through processing has the characteristics of light weight, high strength, corrosion resistance, static resistance and the like.
Description
Technical Field
The invention relates to the technical field of roadway support materials, in particular to a novel mining composite support belt and a preparation process thereof.
Background
The underground tunnel of the coal mine is complex and various in ground stress, surrounding rock stress and deformation, the single anchor bolt support cannot meet the support requirement of the underground tunnel of the coal mine, the tunnel support is generally carried out by adopting an anchor beam system formed by anchor bolts and W steel belts together, and the dispersed plurality of anchor bolts are connected through the W steel belts to form an integral bearing structure, so that the integral effect of the anchor bolt support can be remarkably improved. However, the application of W-steel strip to mine support has some drawbacks.
The W steel strip can generate residual stress in the cold rolling process, so that the deformation and strength of the W steel strip are reduced, the humidity under a mine is high, and metal parts are easy to corrode, so that the W steel strip is easy to corrode and oxidize in the mine environment, and the service life and the safety of the W steel strip are influenced; in addition, the steel density is larger, the W steel belt products are heavier, larger manpower and material resources are required in the transportation and installation processes, the production cost of mines is increased, and meanwhile, the risk of accidental injury to mine workers is increased in the installation process.
Therefore, the light high-strength corrosion-resistant mining composite belt is researched to replace the original W steel belt, and has extremely important significance for mine roadway support. Meanwhile, the mining composite material belt is required to have flame retardant and antistatic properties so as to meet the flame retardant and antistatic requirements of mines on composite material products.
Disclosure of Invention
The invention provides a novel mining composite material supporting belt and a preparation process thereof, which solve the defect that the existing metal supporting belt is easy to corrode, and meanwhile, the composite material supporting belt has the advantages of light weight and high strength, and is easy to transport and install.
The invention is realized by the following technical scheme:
the utility model provides a novel mining composite material support area which characterized in that: the polyurethane is prepared from polyurethane, a flame retardant, oxidized carbon black and glass fiber fabric through a pultrusion process, wherein the polyurethane is prepared by mixing a polyol combination material and isocyanate, and the weight percentages of the raw materials are as follows: 5-10% of polyol composite, 6-16% of isocyanate, 0.3-1% of flame retardant, 0.2-3% of oxidized carbon black and 70-88.5% of glass fiber fabric;
the polyol composition comprises the following components in percentage by mass of 1-4:0.8-1.2:1.1-1.3:0.2-0.3:100, thixotropic agent, dispersant, defoamer and polyol.
Further preferably, the inner mold release agent is one of phosphate, egg phosphoric acid, stearate and triethanolamine oil; the thixotropic agent is one of nano fumed silica, nano activated calcium carbonate and organically modified montmorillonite; the dispersing agent is one of polyester, modified acrylic acid polymer, phosphoric acid and unsaturated carboxylic acid; the defoaming agent is one of silicone oil, polyether ester and organic silicon fluorocarbon; the polyol is polyether polyol or polyester polyol.
Further preferably, the flame retardant is a composite flame retardant consisting of decabromodiphenylethane, antimonous oxide, aluminum hydroxide and tri (2-carboxyethyl) phosphine, and the weight ratio of the flame retardant to the composite flame retardant is 0-3:0-1:0-1:1-5.
The invention also claims a preparation process of the novel mining composite material supporting belt, which comprises the following steps:
(1) Preparation of oxidized carbon black: dispersing pure carbon black in 65wt% concentrated nitric acid, heating, stirring, reacting, filtering, washing with water, oven drying to obtain oxidized carbon black, and pulverizing to obtain oxidized carbon black powder;
(2) Stirring and mixing the flame retardant, the oxidized carbon black and the polyol composite material to obtain a polyol mixture, and respectively filling the polyol mixture and isocyanate into a storage tank of a glue injection machine;
(3) Preparing a composite material supporting belt: and (3) threading the glass fiber fabric on a threading plate according to the structural requirement of the composite material supporting belt, guiding the threading plate into a glue injection box and a die, finally respectively pumping the polyol mixture and the isocyanate to the glue injection box through continuous pumping, fully infiltrating the polyol mixture and the glass fiber, and then entering the die for high-temperature curing and pultrusion.
Further preferably, in the step (1), the addition ratio of the pure carbon black to 65wt% of concentrated nitric acid is 10g:210mL, stirring at 100deg.C for reaction for 12 hr, filtering, washing with water to neutrality, oven drying in vacuum oven at 80deg.C to obtain oxidized carbon black, and grinding the oxidized carbon black to powder with particle diameter below 10 μm.
Further preferably, in the step (2), the polyol mixture is obtained by stirring with an electric stirrer at 2500rpm for 3 minutes.
It is further preferred that in step (3) the weight ratio of isocyanate to polyol blend is from 1:1.1 to 1.4.
Still more preferably, the composite material supporting belt structure is structurally designed according to the submerged supporting working condition, and a uniform-section solid structure is adopted, so that the phenomenon of internal stress concentration of the supporting belt in the bearing process of the composite material supporting belt is avoided, the ultimate bearing capacity of the composite material supporting belt is improved, meanwhile, the uniform-section design can select a pultrusion process with high production efficiency on the production process, the production efficiency of the composite material supporting belt is improved, the cost is reduced, and the popularization of the composite material supporting belt is facilitated; in addition, the composite material supporting belt is required to be perforated to be matched with the anchor rod to carry out roadway supporting, so that two reinforcing ribs are respectively designed on two sides of the supporting belt, and the longitudinal strength loss caused by perforation of the supporting belt is compensated.
The glass fiber fabric is made of a transverse reinforced fiber felt or a 45-degree inclined fiber reinforced felt so as to strengthen the transverse tensile strength of the composite material supporting belt, thereby improving the transverse limit load borne by the composite material supporting belt.
The invention is characterized in that the polyol mixture and isocyanate are injected into a mould according to a proportion, mixed and infiltrated with glass fiber in a mould cavity, and formed into the glass fiber reinforced polyurethane composite material through high-temperature solidification and pultrusion, and finally the composite material support belt obtained through processing has the characteristics of light weight, high strength, corrosion resistance, static resistance and the like.
Drawings
The invention is further described below with reference to the accompanying drawings.
FIG. 1 is a flow chart of the preparation process of the composite support belt of example 1;
FIG. 2 is a schematic cross-sectional view of an embodiment composite support belt;
FIG. 3 is a flow chart of the preparation process of the composite support belt of example 2.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1:
the embodiment provides a novel composite material supporting band which is prepared from the following materials by weight, wherein 3320g of polyol combination material, 4510g of isocyanate, 180g of composite flame retardant, 400g of oxidized carbon black and 26000g of glass fiber fabric.
In the polyol combination material, 42g of phosphate, 30g of nano fumed silica, 40g of modified acrylic polymer, 8g of organosilicon fluorocarbon and 3200g of polyether polyol.
The composite flame retardant is a decabromodiphenylethane, antimonous oxide, aluminum hydroxide and tris (2-carboxyethyl) phosphine composite flame retardant, wherein 54g of decabromodiphenylethane, 18g of antimonous oxide, 18g of aluminum hydroxide and 90g of tris (2-carboxyethyl) phosphine.
A preparation process flow chart of the novel composite material support belt is shown in figure 1.
Firstly, 500g of pure carbon black is dispersed in 10500mL of 65wt% concentrated nitric acid, stirred and reacted for 12 hours at 100 ℃, filtered, washed to be neutral by water, dried in a vacuum drying oven at 80 ℃, and oxidized carbon black is crushed into powder with the particle size of less than 10 mu m;
then 400g of oxidized carbon black and 180g of composite flame retardant are added into 3320g of organic polyol composite material, the mixture is stirred for 3 minutes by an electric stirrer at the rotation speed of 2500rpm, the mixed polyol mixture is obtained, 3900g of polyol mixture and 4510g of isocyanate are respectively added into a storage tank of a glue injection machine, glass fiber fabric is subjected to yarn threading on a yarn threading plate according to the structural requirement of a composite material supporting band, the yarn threading plate is led into a glue injection box and a mould, finally the polyol mixture and the isocyanate are continuously pumped into the glue injection box and fully infiltrated with glass fiber and then enter the mould for high-temperature curing, and the composite material supporting band is formed into the composite material supporting band by pultrusion according to the sectional dimension of the composite material supporting band shown in figure 2.
Example 2:
the embodiment provides a novel composite material supporting band which comprises the following raw materials of 3320g of polyol combination material, 4510g of isocyanate, 120g of composite flame retardant, 400g of oxidized carbon black and 26000g of glass fiber fabric.
In the polyol combination material, 42g of triethanolamine oil, 30g of nano activated calcium carbonate, 40g of polyester dispersing agent, 8g of polyether ester and 3200g of polyester polyol
The composite flame retardant is composed of 36g of decabromodiphenylethane, 12g of antimonous oxide, 12g of aluminum hydroxide and 60g of tri (2-carboxyethyl) phosphine.
The rest of the preparation process is the same as in example 1.
Example 3:
the embodiment of the invention provides a novel composite material support belt which comprises the following raw materials of 3320g of polyol combination material, 4510g of isocyanate, 180g of composite flame retardant and 26000g of glass fiber fabric.
In the polyol combination material, 42g of phosphate, 30g of nano fumed silica, 40g of modified acrylic polymer, 8g of organosilicon fluorocarbon and 3200g of polyether polyol.
The composite flame retardant is composed of decabromodiphenylethane, antimonous oxide, aluminum hydroxide and tri (2-carboxyethyl) phosphine, wherein 54g of decabromodiphenylethane, 18g of antimonous oxide, 18g of aluminum hydroxide and 90g of tri (2-carboxyethyl) phosphine.
A preparation process of a novel composite material supporting belt is shown in a process flow chart of figure 3.
Firstly adding a composite flame retardant into an organic polyol composite material according to a proportion, stirring for 3 minutes by an electric stirrer at a rotating speed of 2500rpm, respectively filling the mixed polyol composite material and isocyanate into a storage tank of a glue injection machine according to the proportion, threading glass fibers and glass fabrics on a threading plate according to the structural requirement of a composite material supporting belt, introducing the glass fibers and the glass fabrics into a glue injection box and a mould, continuously pumping the polyurethane composite material into the glue injection box and the glass fibers to fully infiltrate the polyurethane composite material supporting belt, then entering the mould for high-temperature solidification, carrying out pultrusion to form the composite material supporting belt according to the section size of the composite material supporting belt shown in fig. 2, and finally spraying a non-carbon antistatic coating on the surface of the composite material supporting belt.
The technical properties of the composite support belts obtained in examples 1-3 are compared in the following table:
w steel band technical specification and technical parameters:
it can be seen from the comparison table of the properties of the composite material supporting belts, the composite material supporting belts manufactured according to the embodiment 1, the embodiment 2 and the embodiment 3 of the invention have the characteristics of light weight and high strength, have flame retardant property and antistatic property, meet the corresponding standard requirements, have the tensile strength far greater than that of the W steel belt, have the tensile breaking load greater than that of the W steel belt with the thickness of 5mm, have the tensile breaking load of only 3.5mm, greatly reduce the overall weight of supporting products, facilitate the transportation and installation of workers, and can replace the W steel belt for use. Comparing example 1 with example 2, the flame retardant ratio of example 2 is reduced, so that the flame retardant effect is slightly reduced, but the flame retardant is still compounded with the flame retardant requirement; meanwhile, in the comparative examples 1 and 3, the antistatic agent of the internal mixed carbon type has better antistatic effect than the external coating non-carbon type coating.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (8)
1. The utility model provides a novel mining composite material support area which characterized in that: the polyurethane is prepared from polyurethane, a flame retardant, oxidized carbon black and glass fiber fabric through a pultrusion process, wherein the polyurethane is prepared by mixing a polyol combination material and isocyanate, and the weight percentages of the raw materials are as follows: 5-10% of polyol composite, 6-16% of isocyanate, 0.3-1% of flame retardant, 0.2-3% of oxidized carbon black and 70-88.5% of glass fiber fabric; the polyol combination material is prepared by mixing an inner mold release agent, a thixotropic agent, a dispersing agent, an antifoaming agent and polyol in a mass ratio of 1-4:0.8-1.2:1.1-1.3:0.2-0.3:100.
2. The novel mining composite support strip of claim 1, wherein: the flame retardant is a composite flame retardant of decabromodiphenylethane, antimonous oxide, aluminum hydroxide and tri (2-carboxyethyl) phosphine, and the weight ratio of the flame retardant to the tri (2-carboxyethyl) phosphine is 0-3:0-1:0-1:1-5.
3. The novel mining composite support strip of claim 1, wherein: the inner release agent is one of phosphate, egg phosphoric acid, stearate and triethanolamine oil; the thixotropic agent is one of nano fumed silica, nano activated calcium carbonate and organically modified montmorillonite; the dispersing agent is one of polyester, modified acrylic acid polymer, phosphoric acid and unsaturated carboxylic acid; the defoaming agent is one of silicone oil, polyether ester and organic silicon fluorocarbon; the polyol is polyether polyol or polyester polyol.
4. The process for preparing the novel mining composite support belt as claimed in claim 1, which is characterized by comprising the following steps: (1) Dispersing pure carbon black in 65wt% concentrated nitric acid, heating, stirring, reacting, filtering, washing with water, oven drying to obtain oxidized carbon black, and pulverizing to obtain oxidized carbon black powder; (2) Stirring and mixing the flame retardant, the oxidized carbon black and the polyol composite material to obtain a polyol mixture, and respectively adding the polyol mixture and isocyanate into a storage tank of a glue injection machine; (3) And (3) threading the glass fiber fabric on a threading plate according to the structural requirement of the composite material supporting belt, guiding the threading plate into a glue injection box and a die, finally respectively pumping the polyol mixture and the isocyanate to the glue injection box through continuous pumping, fully infiltrating the polyol mixture and the glass fiber, and then entering the die for high-temperature curing and pultrusion.
5. The process for preparing the novel mining composite supporting strip as claimed in claim 4, wherein: in the step (1), the addition ratio of the pure carbon black to 65wt% of concentrated nitric acid is 10g:210mL, stirring at 100deg.C for reaction for 12 hr, filtering, washing with water to neutrality, oven drying in vacuum oven at 80deg.C to obtain oxidized carbon black, and grinding the oxidized carbon black to powder with particle diameter below 10 μm.
6. The process for preparing the novel mining composite supporting strip as claimed in claim 4, wherein: in the step (2), the mixture is stirred for 3 minutes by an electric stirrer at a rotation speed of 2500rpm, and a mixed polyol composite material is obtained.
7. The process for preparing the novel mining composite supporting strip as claimed in claim 4, wherein: in the step (3), the weight ratio of the polyol mixture to the isocyanate is 1:1.1-1.4.
8. The process for preparing the novel mining composite supporting strip as claimed in claim 4, wherein: in the step (3), the glass fiber fabric is a transverse reinforced fiber felt or an inclined 45-degree fiber reinforced felt, and the composite material support belt structure is a constant-section solid structure.
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| CN111748073A (en) * | 2019-03-26 | 2020-10-09 | 科思创德国股份有限公司 | Method for preparing polyurethane pultrusion composite material |
| CN113999515A (en) * | 2021-12-10 | 2022-02-01 | 南京经略复合材料有限公司 | Glass fiber reinforced polyurethane material, supporting beam and preparation process of supporting beam |
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| CN107345061A (en) * | 2016-05-04 | 2017-11-14 | 科思创聚合物（中国）有限公司 | Pultrusion compound polyurethane material and preparation method thereof |
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