CN112225864A - Nano composite reinforced material and preparation method thereof - Google Patents
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- C—CHEMISTRY; METALLURGY
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- 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
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- 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
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- 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
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- C08G18/58—Epoxy resins
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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- C08K3/34—Silicon-containing compounds
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K9/00—Use of pretreated ingredients
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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Abstract
The invention discloses a nano composite reinforced material and a preparation method thereof, the content of isocyanate adopted is far lower than that of the traditional composite reinforced material, so the heat release amount in the reaction process is reduced, and the dangerous accidents that the reinforced material gathers heat to cause the smoke of coal body and even fires underground when the single-hole grouting amount is large are avoided; the invention adopts the in-situ polymerization method, greatly improves the strength of the reinforcing material by utilizing the unique characteristic combination generated between the nano particles and the polymer, and the material does not foam when meeting water when applied underground, thereby not influencing the strength of the nano composite reinforcing material, ensuring the safety of the material when in use and further ensuring the safety of workers.
Description
Technical Field
The invention belongs to the technical field of composite reinforced materials, and particularly belongs to a nano composite reinforced material and a preparation method thereof.
Background
In the coal mining construction process, due to complex geological conditions of coal mines, disasters such as roof collapse, fire disasters, gas disasters and the like of coal rock mass caving, working faces or roadway roofs happen occasionally, the production efficiency of the coal mine is affected, and serious potential safety hazards are brought to the coal mines. The traditional high polymer material for coal and rock mass reinforcement in coal mines can effectively solve the potential safety hazard problem, but the heat release of the material is large in the using process, the material is directly contacted with the coal mass, the single-hole grouting amount is large, so that a large amount of heat accumulation of the material is caused, the reaction temperature is further increased, the coal mass is very easy to smoke, and even dangerous accidents of underground ignition are caused. In addition, the polymer material for reinforcing coal and rock mass in the traditional coal mine is easy to foam and expand when meeting water, so that the mechanical strength is greatly reduced, and the minimum standard requirement can not be met far away. In order to solve the existing problems of the traditional polymer material for reinforcing coal and rock masses in coal mines, a low-heat-release ultrahigh-strength nano composite reinforcing material for coal mines is produced.
Disclosure of Invention
In order to solve the technical problems that the curing reaction heat release of the high-polymer grouting reinforcement material for the coal mine is high, the foaming strength is low when meeting water and the like in the prior art, the invention provides the nano composite reinforcement material and the preparation method thereof.
In order to achieve the purpose, the invention provides the following technical scheme: a nano composite reinforced material comprises a component A and a component B, wherein the component A comprises the following substances in parts by mass: 150-250 parts of water glass, 30-80 parts of epoxy resin, 5-20 parts of epoxy diluent, 0.1-10 parts of catalyst and 1-5 parts of dissolution promoter;
the component B comprises the following substances in parts by mass: 10-50 parts of diluent and 200-300 parts of nano particle modified prepolymer, wherein the nano particle modified prepolymer comprises modified nano particle oxide and prepolymer; the prepolymer comprises polypropylene glycol and polymethylene polyphenyl polyisocyanate which are dehydrated.
Furthermore, the modulus of the liquid sodium silicate is 2.2-3.0, and the baume degree is 42 DEG Be-50 DEG Be.
Furthermore, the type of the epoxy resin is at least one of E-51, E-44 and E-20; the epoxy diluent is at least one of AGE, 501 and 691 in type.
Further, the catalyst is at least one of dibutyltin dilaurate, triethanolamine, potassium oleate, triethylene diamine, 2,4, 6-tris (dimethylaminomethyl) phenol, organotin and triethylene diamine; the dissolution accelerator is at least one of sodium lauryl sulfate, polyoxyethylene monostearate and polyoxyethylene lauryl ether.
Further, the diluent is at least one of dimethylformamide, dimethyl carbonate and diethylene glycol ethyl ether.
Furthermore, the modified nano particle oxide is 0.5 to 3 parts by weight, and the modified nano particle oxide is modified nano silicon dioxide particles and/or modified nano aluminum oxide particles.
Furthermore, the prepolymer is uniformly mixed by 50 to 150 parts of dehydrated polypropylene glycol with molecular weight of 400 and 100 to 300 parts of polymethylene polyphenyl polyisocyanate.
The invention also provides a preparation method of the nano composite reinforced material, which comprises the following steps:
s1: adding a certain amount of epoxy diluent into epoxy resin, and stirring to obtain an epoxy resin component; adding a dissolving promoter, a catalyst and an epoxy resin component into water glass, and uniformly stirring to obtain a component A;
s2: modifying the nano-oxide particles by adopting a silane coupling agent to obtain silane coupling agent modified nano-oxide particles;
s3: adding the dewatered polypropylene glycol into polymethylene polyphenyl polyisocyanate for mixing reaction to obtain a prepolymer;
s4: adding the modified nano-oxide particles obtained in the step S2 into the prepolymer obtained in the step S3, adding the modified nano-oxide particles into the prepolymer obtained in the step S3, and adding the mixture into the prepolymer2Heating and stirring the mixture under the protective atmosphere to obtain a nano particle modified prepolymer, and adding a diluent into the nano particle modified prepolymer to react to obtain a component B.
S5: and (4) stirring and mixing the component A prepared in the step (S2) and the component B prepared in the step (S4) according to the volume ratio of 1:1, and carrying out curing reaction to obtain the nano composite reinforced material.
Further, in step S2, a silane coupling agent is pretreated, and the pH of the silane coupling agent aqueous solution is adjusted to 4 to 5; dispersing nano oxide particles into the silane coupling agent aqueous solution to obtain a mixed solution, and performing reflux reaction on the mixed solution to obtain a first precursor; sequentially centrifuging, continuously washing with ethanol and drying the first precursor to obtain a second precursor, wherein the second precursor is the silane coupling agent modified nano oxide particles, the mixed solution is subjected to reflux reaction in a four-neck flask, and the reflux reaction is carried out under the reaction condition of refluxing at 80 ℃ for 8 hours; and (3) drying the first precursor for 8h at 60 ℃ in vacuum to obtain a second precursor.
Further, in step S4, stirring for 1-2 h by using ultrasonic waves and a stirrer at the temperature of 80-85 ℃; and reacting the nanoparticle modified prepolymer with a diluent for 3-4 h to obtain a component B.
Compared with the prior art, the invention has at least the following beneficial effects:
compared with the traditional high polymer material for reinforcing coal and rock masses in coal mines, the nano composite reinforcing material obtained by the invention adopts an in-situ polymerization method, the strength of the reinforcing material is greatly improved by utilizing the unique characteristic combination generated between nano particles and polymers, and the component B in the obtained reinforcing material adopts a modified prepolymer, wherein the content of isocyanate is far lower than that of the traditional composite reinforcing material, so that the heat release in the reaction process is reduced, and the dangerous accidents that the reinforcing material gathers heat to cause smoke of coal masses and even catches fire underground when the single-hole grouting amount is large are avoided; and because the epoxy resin is added into the component A, the adhesion of the material is also improved to a certain extent, the mechanical strength of the composite reinforced material is further ensured not to be reduced, and the safety of the reinforced material in use is ensured.
Furthermore, in the underground application of the nano composite reinforced material, after the component A and the component B are uniformly mixed through injection of a grouting pump, the modified prepolymer in the component B can generate carbon dioxide gas when meeting water, but the component A contains water glass, and a large amount of carbon dioxide gas and the water glass can generate curing reaction, so that the reinforced material cannot be foamed when meeting water in the underground application, the strength of the material cannot be influenced when meeting water, the strength of the material cannot be changed, the safety of the material in use is guaranteed, and the safety of workers is further guaranteed.
Furthermore, the modified nano particle oxide adopted by the invention can be more uniformly distributed in the prepolymer, so that the strength of the composite reinforced material obtained by the invention is better enhanced, and the safety of the reinforced material is further ensured.
Furthermore, compared with the traditional polyurethane reinforcing material, the nano composite reinforcing material obtained by the invention is added with water glass with lower price, so that the material cost is greatly reduced, and the preparation method of the nano composite reinforcing material is safe, effective, simple and reliable. Has high commercial value.
Detailed Description
The present invention is described in further detail below with reference to examples, which are provided to illustrate the principles of the present invention and are not intended to limit the scope of the present invention.
The components in the following examples are in parts by mass.
Example 1:
(1) component A
Adding 20 parts of epoxy diluent AGE into 60 parts of epoxy resin E-44, and stirring for 10min to obtain an epoxy resin component with moderate viscosity;
adding 2 parts of dissolution promoting agent sodium lauryl sulfate into 150 parts of water glass, stirring for 30min to a uniform state, adding all the epoxy resin components and 1.5 parts of composite catalyst, and stirring for 30min to a uniform state to obtain a component A, wherein the composite catalyst comprises 0.5 part of organic tin and 1 part of triethylene diamine.
(2) Preparation of component B
Adding 50 parts of dehydrated polypropylene glycol PPG 400 into 250 parts of polymethylene polyphenyl polyisocyanate, uniformly mixing, adding 3 parts of nano silica particles modified by a silane coupling agent KH550, heating to 85 ℃ under the protection of nitrogen, simultaneously stirring for 1h by using ultrasonic waves and a stirrer at the temperature of 85 ℃, uniformly dispersing the modified nano silica particles in the prepolymer to obtain a nanoparticle modified prepolymer, adding 10 parts of diluent dimethylformamide into 300 parts of the nanoparticle modified prepolymer, and continuously reacting for 3h to obtain a component B.
(3) The A, B components are uniformly mixed according to the volume of 1:1, and the nano composite reinforced material can be obtained.
Example 2:
(1) component A
Adding 5 parts of epoxy diluent 501 into 30 parts of epoxy resin E-51, and stirring for 25min to obtain an epoxy resin component with moderate viscosity;
adding 5 parts of dissolution promoting agent polyoxyethylene monostearate into 200 parts of water glass, stirring for 10min to a uniform state, adding all the epoxy resin components and 10 parts of composite catalyst, and stirring for 60min to a uniform state to obtain a component A, wherein the composite catalyst comprises 2 parts of triethanolamine, 3 parts of potassium oleate and 5 parts of 2,4, 6-tris (dimethylaminomethyl) phenol DMP-30.
(2) Preparation of component B
Adding 120 parts of dewatered polypropylene glycol PPG 400 into 100 parts of polymethylene polyphenyl polyisocyanate, uniformly mixing, adding 2 parts of KH550 modified nano alumina particles, heating to 80 ℃ under the protection of nitrogen, simultaneously stirring by using ultrasonic waves and a stirrer at the temperature of 80 ℃ for 2 hours to ensure that the modified nano alumina particles can be uniformly distributed in the prepolymer to obtain a nano particle modified prepolymer, adding 20 parts of diluent dimethyl carbonate into 220 parts of nano particle modified prepolymer, and continuously reacting for 4 hours to obtain a component B.
(3) The A, B components are uniformly mixed according to the volume ratio of 1:1, and the nano composite reinforced material is obtained.
Example 3:
(1) component A
Adding 20 parts of epoxy diluent 691 into 80 parts of epoxy resin E-20, and stirring for 30min to obtain an epoxy resin component with moderate viscosity;
adding 1 part of dissolution promoting agent polyoxyethylene lauryl ether into 250 parts of water glass, stirring for 10min to a uniform state, adding all the epoxy resin components and 3.2 parts of composite catalyst, and stirring for 60min to a uniform state to obtain a component A, wherein the composite catalyst comprises 1.5 parts of organic tin, 0.8 part of potassium oleate and 1g of DMP-30.
(2) Preparation of component B
Adding 150 parts of dewatered polypropylene glycol PPG 400 into 240 parts of polymethylene polyphenyl polyisocyanate, uniformly mixing, adding 0.5 part of KH550 modified nano-silica particles, raising the temperature to 85 ℃ under the protection of nitrogen, simultaneously stirring by using ultrasonic waves and a stirrer for 2 hours to ensure that the nano-silica particles can be uniformly distributed in the prepolymer to obtain a nano-particle modified prepolymer, adding 20 parts of diluent diethylene glycol ethyl ether into 300 parts of the prepolymer, and continuously reacting for 3 hours to obtain a component B.
(3) A, B components are uniformly mixed according to the volume ratio of 1:1, so that the low-heat-release ultrahigh-strength nano composite reinforced material can be obtained.
Example 4
(1) Component A
Adding 20 parts of AGE and 501 mixed epoxy diluent into 60 parts of E-44 and E-51 mixed epoxy resin, and stirring for 20min to obtain an epoxy resin component with moderate viscosity;
adding 2 parts of sodium lauryl sulfate and polyoxyethylene lauryl ether composite dissolution accelerator into 150 parts of water glass, stirring for 30min to a uniform state, adding all the epoxy resin components and 0.1 part of catalyst dibutyltin dilaurate, and stirring for 30min to a uniform state to obtain the component A.
(2) Preparation of component B
Adding 50 parts of dewatered polypropylene glycol PPG 400 into 250 parts of polymethylene polyphenyl polyisocyanate, uniformly mixing, adding 3 parts of nano silica particles and nano alumina particles modified by a silane coupling agent KH550, heating to 85 ℃ under the protection of nitrogen, simultaneously stirring by using ultrasonic waves and a stirrer at 85 ℃ for 1h to uniformly disperse the modified nano silica particles and the nano alumina particles in the prepolymer to obtain a nano particle modified prepolymer, adding 10 parts of dimethylformamide and diethylene glycol diethyl ether mixed diluent into 300 parts of nano particle modified prepolymer, and continuously reacting for 3h to obtain a component B.
(3) The A, B components are uniformly mixed according to the volume of 1:1, and the nano composite reinforced material can be obtained.
Example 5
(1) Component A
Adding 5 parts of epoxy diluent 501 and 691 mixed epoxy diluent into 30 parts of E-51 and E-20 mixed epoxy resin, and stirring for 25min to obtain an epoxy resin component with moderate viscosity;
adding 5 parts of polyoxyethylene monostearate and polyoxyethylene lauryl ether composite dissolution promoter into 200 parts of water glass, stirring for 10min to a uniform state, adding all the epoxy resin components and 5 parts of composite catalyst, and stirring for 60min to a uniform state to obtain a component A, wherein the composite catalyst comprises 2 parts of triethanolamine and 3 parts of triethylene diamine.
(2) Preparation of component B
Adding 120 parts of dewatered polypropylene glycol PPG 400 into 100 parts of polymethylene polyphenyl polyisocyanate, uniformly mixing, adding 2 parts of KH550 modified nano alumina particles, heating to 80 ℃ under the protection of nitrogen, simultaneously stirring by using ultrasonic waves and a stirrer at the temperature of 80 ℃ for 2 hours to ensure that the modified nano alumina particles can be uniformly distributed in the prepolymer to obtain a nano particle modified prepolymer, adding 20 parts of dimethyl carbonate and dimethyl formamide mixed diluent into 220 parts of nano particle modified prepolymer, and continuously reacting for 4 hours to obtain a component B.
(3) The A, B components are uniformly mixed according to the volume ratio of 1:1, and the nano composite reinforced material is obtained.
Example 6
(1) Component A
Adding 20 parts of 691 and AGE mixed epoxy diluent into 80 parts of E-20 and E-44 mixed epoxy resin, and stirring for 30min to obtain an epoxy resin component with moderate viscosity;
adding 1 part of dissolution promoting agent polyoxyethylene lauryl ether into 250 parts of water glass, stirring for 10min to a uniform state, adding all the epoxy resin components and 5.6 parts of composite catalyst, and stirring for 60min to a uniform state to obtain a component A, wherein the composite catalyst comprises 2 parts of triethanolamine, 2 parts of triethylene diamine and 1.6g of DMP-30.
(2) Preparation of component B
Adding 150 parts of dewatered polypropylene glycol PPG 400 into 240 parts of polymethylene polyphenyl polyisocyanate, uniformly mixing, adding 0.5 part of KH550 modified nano-silica particles, heating to 85 ℃ under the protection of nitrogen, simultaneously stirring by using ultrasonic waves and a stirrer for 2 hours to ensure that the nano-silica particles can be uniformly distributed in the prepolymer to obtain a nano-particle modified prepolymer, adding 20 parts of diethylene glycol ethyl ether and dimethyl carbonate mixed diluent into 300 parts of the nano-particle modified prepolymer, and continuously reacting for 3 hours to obtain a component B.
(3) A, B components are uniformly mixed according to the volume ratio of 1:1, so that the low-heat-release ultrahigh-strength nano composite reinforced material can be obtained.
The composite material obtained in the above embodiment was subjected to performance test with a polymer material for coal mine reinforcement coal rock according to standard AQ 1089-:
TABLE 1 nanocomposite reinforcement Performance results
| Item | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 |
| Maximum reaction temperature/. degree.C | 91 | 85 | 88 | 85 | 87 | 91 |
| Compressive strength/MPa | 73 | 75 | 76 | 72 | 73 | 72 |
| Tensile strength/MPa | 31 | 27 | 26 | 31 | 32 | 25 |
| Shear strength/MPa | 36 | 39 | 37 | 33 | 36 | 33 |
| Adhesive strength/MPa | 8.9 | 8.5 | 9.3 | 8.2 | 8.6 | 8.5 |
| Expansion ratio/times | 1.1 | 1.1 | 1.1 | 1.05 | 1.1 | 1.2 |
The highest reaction temperature of the traditional organic reinforcing material is as high as 140 ℃, and compared with the traditional organic reinforcing material (AQ 1089-;
as can be seen from Table 1, the expansion rate of the nanocomposite reinforced material is low, only 1.1 times, and far lower than that of the conventional organic reinforced material after meeting water, so that the aim of non-foaming of the nanocomposite reinforced material when meeting water is fulfilled;
from table 1, it can be seen that the nanocomposite reinforced material obtained by the invention has higher strength, the highest compressive strength of which reaches 76MPa, the highest tensile strength of which reaches 32MPa, the highest shear strength of which reaches 39MPa, and the highest bonding strength of which reaches 9.3MPa, which are far higher than the performance requirements of the polymer materials C and R for the coal and rock reinforcement of the standard AQ 1089-.
Claims (10)
1. The nano composite reinforced material is characterized by comprising a component A and a component B, wherein the component A comprises the following substances in parts by mass: 150-250 parts of water glass, 30-80 parts of epoxy resin, 5-20 parts of epoxy diluent, 0.1-10 parts of catalyst and 1-5 parts of dissolution promoter;
the component B comprises the following substances in parts by mass: 10-50 parts of diluent and 200-300 parts of nano particle modified prepolymer, wherein the nano particle modified prepolymer comprises modified nano particle oxide and prepolymer; the prepolymer comprises polypropylene glycol and polymethylene polyphenyl polyisocyanate which are dehydrated.
2. The nanocomposite reinforcement according to claim 1, characterized in that the liquid sodium silicate has a modulus of 2.2 to 3.0 and a baume degree of 42 ° baue to 50 ° baue.
3. The nanocomposite reinforced material of claim 1, wherein the epoxy resin is at least one of type E-51, E-44, and E-20; the epoxy diluent is at least one of AGE, 501 and 691 in type.
4. The nanocomposite reinforcement material of claim 1, wherein the catalyst is at least one of dibutyltin dilaurate, triethanolamine, potassium oleate, triethylenediamine, 2,4, 6-tris (dimethylaminomethyl) phenol, organotin, triethylenediamine; the dissolution accelerator is at least one of sodium lauryl sulfate, polyoxyethylene monostearate and polyoxyethylene lauryl ether.
5. The nanocomposite reinforcement material of claim 1, wherein the diluent is at least one of dimethylformamide, dimethyl carbonate, and diethylene glycol ethyl ether.
6. The nanocomposite reinforced material of claim 1, wherein the modified nanoparticle oxide is 0.5 to 3 parts by weight, and the modified nanoparticle oxide is modified nano silica particles and/or modified nano alumina particles.
7. The nanocomposite reinforced material of claim 1, wherein the prepolymer is prepared by uniformly mixing 50 to 150 parts of water-removed polypropylene glycol with a molecular weight of 400 and 100 to 300 parts of polymethylene polyphenyl polyisocyanate.
8. A method for preparing a nanocomposite reinforced material according to claims 1 to 7, comprising the following steps:
s1: adding a certain amount of epoxy diluent into epoxy resin, and stirring to obtain an epoxy resin component; adding a dissolving promoter, a catalyst and an epoxy resin component into water glass, and uniformly stirring to obtain a component A;
s2: modifying the nano-oxide particles by adopting a silane coupling agent to obtain silane coupling agent modified nano-oxide particles;
s3: adding the dewatered polypropylene glycol into polymethylene polyphenyl polyisocyanate for mixing reaction to obtain a prepolymer;
s4: adding the modified nano-oxide particles obtained in the step S2 into the prepolymer obtained in the step S3, adding the modified nano-oxide particles into the prepolymer obtained in the step S3, and adding the mixture into the prepolymer2Heating and stirring under a protective atmosphere to obtain a nanoparticle modified prepolymer, and adding a diluent into the nanoparticle modified prepolymer to react to obtain a component B;
s5: and (4) stirring and mixing the component A prepared in the step (S2) and the component B prepared in the step (S4) according to the volume ratio of 1:1, and carrying out curing reaction to obtain the nano composite reinforced material.
9. The method according to claim 8, wherein in step S2, the silane coupling agent is pretreated to adjust the pH of the aqueous solution of the silane coupling agent to 4 to 5; dispersing nano oxide particles into the silane coupling agent aqueous solution to obtain a mixed solution, and performing reflux reaction on the mixed solution to obtain a first precursor; sequentially centrifuging, continuously washing with ethanol and drying the first precursor to obtain a second precursor, wherein the second precursor is the silane coupling agent modified nano oxide particles, the mixed solution is subjected to reflux reaction in a four-neck flask, and the reflux reaction is carried out under the reaction condition of refluxing at 80 ℃ for 8 hours; and (3) drying the first precursor for 8h at 60 ℃ in vacuum to obtain a second precursor.
10. The method according to claim 8, wherein in step S4, the stirring is performed at 80 ℃ to 85 ℃ for 1h to 2h by using ultrasonic waves and a stirrer simultaneously; and reacting the nanoparticle modified prepolymer with a diluent for 3-4 h to obtain a component B.
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