A polymer composite foam material for plugging boreholes in mines and its preparation method

Abstract

A polymer composite foam material for plugging boreholes in mines and its preparation method belong to the technical field of borehole sealing for gas drainage in mines. The polymer composite foam material is composed of component A composition and component B composition. Among them, for component A: 110 - 120 parts of PAPI, 6 - 10 parts of flame retardant MCA, 1 - 3 parts of polymer foaming microspheres, 1 - 3 parts of light calcium carbonate powder, 2 - 5 parts of conductive carbon black powder, 2 - 5 parts of diethylene glycol dibenzoate, 2 - 3 parts of YRFC-RG01 thixotropic agent. For component B: 45 - 50 parts of 4110 polyether, 45 - 50 parts of 635 polyether, 1 - 3 parts of 403 polyether, 2 - 3 parts of foam stabilizer, 10 - 15 parts of foaming agent, 5 - 10 parts of flame retardant MP, 10 - 12 parts of DMMP flame retardant, 0.5 - 1.0 part of composite catalyst, 3 - 5 parts of antistatic agent, 1 - 3 parts of aluminum hydroxide powder, 2 - 3 parts of YRFC-RG02A thixotropic agent. This material has excellent borehole sealing function and is mainly used for rapid plugging of gas boreholes in coal mines.

Description

Technical Field

[0001] The present invention belongs to the technical field of hole - sealing for mine gas drainage boreholes, and mainly relates to a polymer composite foam material for plugging mine boreholes and a preparation method thereof. This material has excellent hole - sealing functions and is mainly applied to the rapid plugging of gas boreholes in coal mines. Background Technique

[0002] Coal mine gas drainage is the fundamental way to solve the mine gas problem. The hole - sealing quality of boreholes is one of the key factors affecting the gas drainage effect. After the borehole construction is completed, the work in the hole - sealing link is crucial. During the foaming process of traditional polymer - sprayed foam hole - sealing materials, it is a four - way foaming, with the direction not concentrated. First, it foams on the plane and then foams longitudinally. When there is no cave - in in the orifice section of the borehole, the hole - sealing effect is better. In the case of serious cave - in, the existing polymer hole - sealing is prone to cause incomplete sealing in the inner plug, shrinkage after hole - sealing forming, the slurry flowing into the borehole during negative - angle borehole grouting, and the grouting pressure cannot rise, so that the hole - sealing section cannot be filled solidly, resulting in poor hole - sealing quality, directly affecting the borehole drainage effect, unable to effectively reduce the coal - seam gas content, and restricting the safe and efficient production of coal mines.

[0003] Based on the existing problems, the present invention proposes a polymer composite foam material for plugging mine boreholes with a high foaming multiple and excellent expansibility and a preparation method thereof, which mainly solves the problem of incomplete sealing in the inner plug when the borehole collapses, can plug the hole - sealing section tightly, improve the pressure - bearing grouting ability, thereby ensuring the hole - sealing quality of the borehole and improving the drainage effect. Summary of the Invention

[0004] The purpose of the present invention is to provide a polymer composite foam material for plugging mine boreholes and a preparation method thereof in view of the problems existing in the above - mentioned prior art.

[0005] Before forming, the polymer composite foam material is composed of component A composition and component B composition, and the following are in parts by mass; wherein

[0006] Component A:

[0007] 110 - 120 parts of PAPI, 6 - 10 parts of flame retardant MCA, 1 - 3 parts of polymer foaming microspheres, 1 - 3 parts of light calcium carbonate powder, 2 - 5 parts of conductive carbon black powder, 2 - 5 parts of diethylene glycol dibenzoate, 2 - 3 parts of YRFC - RG01 thixotropic agent.

[0008] Component B:

[0009] 4110 polyether: 45 - 50 parts, 635 polyether: 45 - 50 parts, 403 polyether: 1 - 3 parts, foam stabilizer: 2 - 3 parts, foaming agent: 10 - 15 parts, flame retardant MP: 5 - 10 parts, DMMP flame retardant: 10 - 12 parts, composite catalyst: 0.5 - 1.0 part, antistatic agent: 3 - 5 parts, aluminum hydroxide powder: 1 - 3 parts, YRFC - RG02A thixotropic agent: 2 - 3 parts.

[0010] In a further preferred embodiment, the PAPI is polyphenyl polymethylene polyisocyanate with an -NCO group mass content of 31.1 - 31.5%, produced by Wanhua Chemical Group Co., Ltd.; the flame retardant MCA is white crystalline fine powder melamine cyanurate, a commercially available flame retardant with an average particle size of less than 50 microns; the polymer foaming microspheres are produced by AkzoNobel of the Netherlands, model 551DE40D42; the diethylene glycol dibenzoate is commercially available; the thixotropic agent is YRFC - RG01 and YRFC - RG02A thixotropic agents produced by Guangzhou Yourun; the conductive carbon black powder and light calcium carbonate powder are commercially available with an average particle size of less than 10 microns and are dried before use.

[0011] In a further preferred embodiment, the 4110 polyether, 635 polyether, and 403 polyether are polyether polyols produced by Hebei Yadong Chemical Group Co., Ltd.; the foam stabilizer is L - 6900 type polyurethane rigid foam stabilizer produced by Momentive Performance Materials Inc. of the United States; the antistatic agent is Ortegol - AST type antistatic agent produced by Goldschmidt of Germany; the foaming agent model HFO - 1336mzzZ is cis - hexafluorobutene, sold by fluorine chemical refrigerant distributors; the flame retardant MP is commercially available melamine phosphate with an average particle size of less than 50 microns; the DMMP flame retardant is commercially available dimethyl methylphosphonate; the aluminum hydroxide powder has an average particle size of less than 10 microns and is commercially available.

[0012] The preparation method of the further composite catalyst is to dissolve 40 parts of triethylenediamine in 60 parts of diethylene glycol solvent at room temperature, and then add 4 parts of dibutyltin dilaurate solution thereto, and stir and mix evenly.

[0013] The preparation method of the above polymer composite foam material for plugging boreholes of the present invention is prepared according to the following steps:

[0014] First step, preparation of component A:

[0015] Step 1: Add 110 - 120 parts of PAPI, 6 - 10 parts of flame retardant MCA, 1 - 3 parts of polymer foaming microspheres, 1 - 3 parts of light calcium carbonate powder, and 2 - 5 parts of conductive carbon black powder into a mixing container in sequence, and stir and mix evenly at room temperature under nitrogen protection, with a stirring rate of 30 - 40 r / min;

[0016] Step 2: Then, add 2 - 5 parts of diethylene glycol dibenzoate and 2 - 3 parts of YRFC - RG01 thixotropic agent to the above - mentioned mixed materials, and continue stirring for 20 minutes to obtain Component A.

[0017] Step 3: Fill Component A into one end of a plastic soft - packaging bag according to the measurement. The middle of the plastic soft - packaging bag is sealed and separated by a plastic clip, and then it is sealed with a sealing machine under nitrogen protection.

[0018] Second step: Preparation of Component B:

[0019] Step 1: Add 45 - 50 parts of polyether 4110, 45 - 50 parts of polyether 635, and 1 - 3 parts of polyether 403 into the mixing kettle in sequence. Under the condition that the stirring rate is 30 - 40 r / min, stir evenly at normal temperature.

[0020] Step 2: Then add 2 - 3 parts of foam stabilizer, 10 - 12 parts of DMMP flame retardant, and 0.5 - 1.0 part of composite catalyst, and stir further evenly.

[0021] Step 3: Then add 5 - 10 parts of flame retardant MP, 3 - 5 parts of antistatic agent, and 1 - 3 parts of aluminum hydroxide powder into the mixing kettle and stir evenly.

[0022] Step 4: Finally, add 2 - 3 parts of YRFC - RG02A thixotropic agent and 10 - 15 parts of foaming agent, and stir and mix evenly at normal temperature to obtain Component B.

[0023] Step 5: Fill Component B into the other end of the plastic soft - packaging bag according to the measurement. The middle of the plastic soft - packaging bag is sealed and separated by a plastic clip, and then it is sealed with a sealing machine under nitrogen protection.

[0024] Load A and B according to the mass ratio A∶B = 1 - 1.05∶1.

[0025] Third step: Preparation of the polymer composite foam material for plugging boreholes:

[0026] Step 1: Manually squeeze and knead the plastic soft - packaging bags containing the A and B composition components respectively to make the A and B components in the bags in a flowing state.

[0027] Step 2: Extract the middle plastic clip of the plastic soft - packaging bag, squeeze and knead the A and B components in the soft - packaging plastic bag for 30 - 60 s, and then fill the plastic soft - packaging bag into the borehole. The A and B components undergo a polymerization reaction to generate the polymer composite foam material for plugging the borehole.

[0028] The plastic soft - packaging bag and the plastic clip are provided by Shanxi Synthetic Materials Industry Technology Research Institute Co., Ltd.

[0029] Compared with the prior art, the present invention has the following advantages:

[0030] First, the present invention adds solid flame retardants MCA and MP, and solid fillers light calcium carbonate powder and aluminum hydroxide powder to components A and B, which play a role of skeleton and reinforcement in the generated polymer foam, and can prevent the shrinkage of the polymer after molding;

[0031] Second, the present invention adds polymer foaming microspheres of polyacrylate type to the polymerization system. On the one hand, it can fully ensure the foaming ratio of the generated polymer and play a role of secondary foaming. On the other hand, it can increase the strength of the polymer foam material and also prevent the shrinkage of the polymer foam material.

[0032] Third, the present invention adds a thixotropic agent to components A and B, making the A and B composition materials in a physical gel state during storage, which can effectively prevent the sedimentation and caking of solid materials in components A and B during storage in soft packaging plastic bags, ensuring the uniform dispersion of solid materials in the system during the subsequent polymerization process and the stress dispersion effect in the foam material;

[0033] Fourth, the addition of conductive carbon black powder and antistatic agent ensures the good antistatic property of the polymer foam material after molding, which is beneficial to the safety of gas pipeline sealing and the safe production of coal mines.

[0034] Fifth, the use of the environmentally friendly foaming agent cis-hexafluorobutene ensures the foaming ratio while not damaging the ozone layer, has good safety performance, is not flammable, does not explode, is non-toxic, non-irritating, and non-corrosive. Detailed implementation manners

[0035] Example 1

[0036] The polymer composite foam material for plugging boreholes in this example consists of components A and B with the following mass parts before molding:

[0037] Component A:

[0038] 110 parts of PAPI, 10 parts of flame retardant MCA, 3 parts of polymer foaming microspheres, 3 parts of light calcium carbonate powder, 5 parts of conductive carbon black powder, 5 parts of diethylene glycol dibenzoate, 3 parts of YRFC-RG01 thixotropic agent.

[0039] Component B:

[0040] 45 parts of 4110 polyether, 45 parts of 635 polyether, 3 parts of 403 polyether, 3 parts of foam stabilizer, 15 parts of foaming agent, 10 parts of flame retardant MP, 12 parts of DMMP flame retardant, 1.0 part of composite catalyst, 5 parts of antistatic agent, 3 parts of aluminum hydroxide powder, 3 parts of YRFC-RG02A thixotropic agent.

[0041] Further preferred solution: the PAPI is polyphenyl polymethylene polyisocyanate with an -NCO group mass content of 31.1 - 31.5%, produced by Wanhua Chemical Group Co., Ltd.; the flame retardant MCA is white crystalline fine powder melamine cyanurate, a commercially available flame retardant with an average particle size of less than 50 microns; the polymer foaming microspheres are produced by AkzoNobel of the Netherlands, model 551DE40D42; the diethylene glycol dibenzoate is commercially available; the thixotropic agent is YRFC-RG01 and YRFC-RG02A type thixotropic agents produced by Guangzhou Yourun; the conductive carbon black powder and light calcium carbonate powder are commercially available with an average particle size of less than 10 microns and are dried before use.

[0042] Further preferred solution: the 4110 polyether, 635 polyether, and 403 polyether are polyether polyols produced by Hebei Yadong Chemical Group Co., Ltd.; the foam stabilizer is L-6900 type polyurethane rigid foam stabilizer produced by Momentive Performance Materials Inc. of the United States; the antistatic agent is Ortegol-AST type antistatic agent produced by Goldschmidt of Germany; the blowing agent is 1,1,1,4,4,4-hexafluoro-2-butene, model HFO-1336mzzZ, sold by fluorine chemical refrigerant distributors; the flame retardant MP is commercially available melamine phosphate with an average particle size of less than 50 microns; the DMMP flame retardant is commercially available dimethyl methylphosphonate; the aluminum hydroxide powder has an average particle size of less than 10 microns and is commercially available.

[0043] For the preparation method of the further composite catalyst, 40 parts of triethylenediamine are dissolved in 60 parts of diethylene glycol solvent at room temperature, and then 4 parts of dibutyltin dilaurate solution are added thereto and stirred and mixed evenly.

[0044] The preparation method of the above polymer composite foam material for plugging boreholes in mines of the present invention is prepared according to the following steps:

[0045] First step, preparation of component A:

[0046] Step 1: 110 parts of PAPI, 10 parts of flame retardant MCA, 3 parts of polymer foaming microspheres, 5 parts of conductive carbon black powder, and 3 parts of light calcium carbonate powder are sequentially added to a mixing container and stirred and mixed evenly at room temperature under nitrogen protection, and the stirring rate is 30 - 40 r / min;

[0047] Step 2: Then 5 parts of diethylene glycol dibenzoate and 3 parts of YRFC-RG01 thixotropic agent are added to the above mixed materials and stirred for another 20 minutes to obtain component A;

[0048] Step 3: Meter and load Component A into one end of a plastic soft packaging bag. Seal and separate the middle part of the plastic soft packaging bag with a plastic clip, and then seal it with a sealing machine under nitrogen protection.

[0049] Second step, preparation of Component B:

[0050] Step 1: Add 45 parts of polyether 4110, 45 parts of polyether 635, and 3 parts of polyether 403 into the mixing kettle in sequence. Stir evenly at normal temperature under the condition that the stirring rate is 30 - 40 r / min.

[0051] Step 2: Then add 3 parts of foam stabilizer, 12 parts of DMMP flame retardant, and 1.0 part of composite catalyst, and stir evenly further.

[0052] Step 3: Add 10 parts of flame retardant MP, 5 parts of antistatic agent, and 3 parts of aluminum hydroxide powder into the mixing kettle and stir evenly.

[0053] Step 4: Finally, add 3 parts of YRFC - RG02A thixotropic agent and 15 parts of foaming agent, and stir and mix evenly at normal temperature to obtain Component B.

[0054] Step 5: Meter and load Component B into the other end of the plastic soft packaging bag. Seal and separate the middle part of the plastic soft packaging bag with a plastic clip, and then seal it with a sealing machine under nitrogen protection.

[0055] A and B are loaded according to the mass ratio A∶B = 1 - 1.05∶1, and a mine gas pipeline sealing bag filled with A and B combined materials.

[0056] The plastic soft packaging bag and the plastic clip are provided by Shanxi Synthetic Materials Industry Technology Research Institute Co., Ltd.

[0057] Third step, preparation of the polymer composite foam material for plugging boreholes:

[0058] Step 1: At normal temperature, squeeze and knead the plastic soft packaging bags containing Components A and B by hand respectively to make Components A and B in the bags in a flowing state.

[0059] Step 2: Extract the middle plastic clip of the plastic soft packaging bag, squeeze and knead Components A and B in the plastic soft packaging bag for 30 - 60 s, and then fill the plastic soft packaging bag into the borehole. Components A and B generate a polymer composite material for plugging the borehole through a polymerization reaction.

[0060] Example 2

[0061] For the polymer composite material for plugging boreholes in this example, before molding, it consists of A and B composition components including the following mass parts:

[0062] Component A:

[0063] 120 parts of PAPI, 6 parts of flame retardant MCA, 1 part of polymer foaming microspheres, 1 part of light calcium carbonate powder, 2 parts of conductive carbon black powder, 2 parts of diethylene glycol dibenzoate, 2 parts of YRFC-RG01 thixotropic agent.

[0064] Component B:

[0065] 50 parts of 4110 polyether, 50 parts of 635 polyether, 1 part of 403 polyether, 2 parts of foam stabilizer, 10 parts of foaming agent, 5 parts of flame retardant MP, 10 parts of DMMP flame retardant, 0.5 part of composite catalyst, 3 parts of antistatic agent, 1 part of aluminum hydroxide powder, 2 parts of YRFC-RG02A thixotropic agent.

[0066] In a further preferred embodiment, the PAPI is polyphenyl polymethylene polyisocyanate with a mass content of -NCO groups of 31.1 - 31.5%, produced by Wanhua Chemical Group Co., Ltd.; the flame retardant MCA is white crystalline fine powder melamine cyanurate, a commercially available flame retardant with an average particle size of less than 50 microns; the polymer foaming microspheres are produced by AkzoNobel of the Netherlands, model 551DE40D42; the diethylene glycol dibenzoate is commercially available; the thixotropic agents are YRFC-RG01 and YRFC-RG02A thixotropic agents produced by Guangzhou Yourun; the conductive carbon black powder and the light calcium carbonate powder are commercially available with an average particle size of less than 10 microns and are dried before use.

[0067] In a further preferred embodiment, the 4110 polyether, 635 polyether, and 403 polyether are polyether polyols produced by Hebei Yadong Chemical Group Co., Ltd.; the foam stabilizer is L-6900 type polyurethane rigid foam stabilizer produced by Momentive Performance Materials Inc. of the United States; the antistatic agent is Ortegol-AST type antistatic agent produced by Goldschmidt of Germany; the foaming agent is cis-hexafluorobutene, model HFO-1336mzzZ, sold by fluorine chemical refrigerant distributors; the flame retardant MP is commercially available melamine phosphate with an average particle size of less than 50 microns; the DMMP flame retardant is commercially available dimethyl methylphosphonate; the aluminum hydroxide powder is commercially available with an average particle size of less than 10 microns.

[0068] The preparation method of the further composite catalyst is to dissolve 40 parts of triethylenediamine in 60 parts of diethylene glycol solvent at room temperature, and then add 4 parts of dibutyltin dilaurate solution thereto and stir and mix evenly.

[0069] The preparation method of the above polymer composite material for plugging boreholes of the present invention is prepared according to the following steps:

[0070] First step, preparation of Component A:

[0071] Step 1: Add 120 parts of PAPI, 6 parts of flame retardant MCA, 1 part of polymer foaming microspheres, 2 parts of conductive carbon black powder, and 1 part of light calcium carbonate powder into a mixing container in sequence, and stir and mix evenly at normal temperature under nitrogen protection. The stirring rate is 30 - 40 r / min;

[0072] Step 2: Then add 2 parts of diethylene glycol dibenzoate and 2 parts of YRFC - RG01 thixotropic agent into the above - mentioned mixed materials, and continue to stir for 20 minutes to obtain Component A;

[0073] Step 3: Fill Component A into one end of a plastic soft - packaging bag according to the measurement. The middle of the plastic soft - packaging bag is sealed and separated by a plastic clip, and then sealed with a sealing machine under nitrogen protection.

[0074] Second step: Preparation of Component B:

[0075] Step 1: Add 50 parts of 4110 polyether, 50 parts of 635 polyether, and 1 part of 403 polyether into a mixing kettle in sequence, and stir and mix evenly at normal temperature under the condition that the stirring rate is 30 - 40 r / min;

[0076] Step 2: Then add 2 parts of foam stabilizer, 10 parts of DMMP flame retardant, and 0.5 part of composite catalyst, and further stir and mix evenly;

[0077] Step 3: Then add 5 parts of flame retardant MP, 3 parts of antistatic agent, and 1 part of aluminum hydroxide powder into the mixing kettle and stir evenly;

[0078] Step 4: Finally, add 2 parts of YRFC - RG02A thixotropic agent and 10 parts of foaming agent, and stir and mix evenly at normal temperature to obtain Component B;

[0079] Step 5: Fill Component B into the other end of the plastic soft - packaging bag according to the measurement. The middle of the plastic soft - packaging bag is sealed and separated by a plastic clip, and then sealed with a sealing machine under nitrogen protection.

[0080] Charge A and B according to the mass ratio A∶B = 1 - 1.05∶1. The mine gas pipeline sealing bag filled with A and B combined materials is shown as follows.

[0081] The plastic soft - packaging bag and the plastic clip are provided by Shanxi Synthetic Materials Industry Technology Research Institute Co., Ltd.

[0082] Third step: Preparation of the polymer composite foam material for plugging boreholes:

[0083] Step 1: At normal temperature, squeeze and knead the plastic soft - packaging bags filled with Components A and B by hand respectively to make the A and B components in the bags in a flowing state;

[0084] Step 2: Extract the middle plastic clip of the plastic soft packaging bag, knead and mix components A and B in the plastic soft packaging bag for 30 - 60 s, and then fill the plastic soft packaging bag into the drill hole. Through the polymerization reaction of components A and B, a polymer composite foam material for plugging the drill hole is generated.

[0085] Example 3

[0086] For the polymer composite material for plugging drill holes in this example, before molding, it is composed of A and B composition components including the following mass parts:

[0087] Component A:

[0088] 115 parts of PAPI, 8 parts of flame retardant MCA, 2 parts of polymer foaming microspheres, 2 parts of light calcium carbonate powder, 4 parts of conductive carbon black powder, 3 parts of diethylene glycol dibenzoate, 2 parts of YRFC - RG01 thixotropic agent.

[0089] Component B:

[0090] 47 parts of 4110 polyether, 47 parts of 635 polyether, 2 parts of 403 polyether, 3 parts of foam stabilizer, 13 parts of foaming agent, 8 parts of flame retardant MP, 11 parts of DMMP flame retardant, 0.8 part of composite catalyst, 4 parts of antistatic agent, 2 parts of aluminum hydroxide powder, 2 parts of YRFC - RG02A thixotropic agent.

[0091] In a further preferred solution, the PAPI is polyphenyl polymethylene polyisocyanate, the mass content of -NCO group is 31.1 - 31.5%, produced by Wanhua Chemical Group Co., Ltd.; the flame retardant MCA is white crystalline fine powder melamine cyanurate, a commercially available flame retardant, with an average particle size of less than 50 microns; the polymer foaming microspheres are produced by AkzoNobel of the Netherlands, model 551DE40D42; the diethylene glycol dibenzoate is commercially available; the thixotropic agents are YRFC - RG01 and YRFC - RG02A thixotropic agents produced by Guangzhou Yourun; the conductive carbon black powder and light calcium carbonate powder are commercially available, with an average particle size of less than 10 microns, and are dried before use.

[0092] Further preferred solution: the 4110 polyether, 635 polyether, and 403 polyether are polyether polyols produced by Hebei Yadong Chemical Group Co., Ltd.; the foam stabilizer is the L-6900 type polyurethane rigid foam stabilizer produced by Momentive Performance Materials Inc. of the United States; the antistatic agent is the Ortegol-AST type antistatic agent produced by Goldschmidt AG of Germany; the blowing agent model HFO-1336mzzZ is cis-hexafluorobutene, sold by fluorine chemical refrigerant distributors; the flame retardant MP is melamine phosphate available on the market, with an average particle size of less than 50 microns; the DMMP flame retardant is dimethyl methylphosphonate available on the market; the aluminum hydroxide powder is available on the market, with an average particle size of less than 10 microns.

[0093] Further, the preparation method of the composite catalyst is to dissolve 40 parts of triethylenediamine in 60 parts of diethylene glycol solvent at room temperature, and then add 4 parts of dibutyltin dilaurate solution thereto, and stir and mix evenly.

[0094] The preparation method of the above polymer composite foam material for plugging boreholes of the present invention is prepared according to the following steps:

[0095] The first step, preparation of component A:

[0096] Step 1: Add 115 parts of PAPI, 8 parts of flame retardant MCA, 2 parts of polymer foaming microspheres, 2 parts of light calcium carbonate powder, and 4 parts of conductive carbon black powder into a mixing container in sequence, and stir and mix evenly at room temperature under nitrogen protection, with a stirring rate of 30-40 r / min;

[0097] Step 2: Then add 3 parts of diethylene glycol dibenzoate and 2 parts of YRFC-RG01 thixotropic agent into the above mixed materials, and continue to stir for 20 minutes to obtain component A;

[0098] Step 3: Fill component A into one end of a plastic soft packaging bag according to the measurement, close and separate the middle of the plastic soft packaging bag with a plastic clip, and then seal it with a sealing machine under nitrogen protection.

[0099] The second step, preparation of component B:

[0100] Step 1: Add 47 parts of 4110 polyether, 47 parts of 635 polyether, and 2 parts of 403 polyether into a mixing kettle in sequence, and stir and mix evenly at room temperature under the condition of a stirring rate of 30-40 r / min;

[0101] Step 2: Then add 3 parts of foam stabilizer, 11 parts of DMMP flame retardant, and 0.8 part of composite catalyst, and further stir and mix evenly;

[0102] Step 3: Then add 8 parts of flame retardant MP, 4 parts of antistatic agent, and 2 parts of aluminum hydroxide powder into the mixing kettle and stir evenly;

[0103] Step 4: Finally, add 2 parts of YRFC-RG02A thixotropic agent and 13 parts of foaming agent, and stir and mix evenly at room temperature to obtain Component B;

[0104] Step 5: Fill Component B into the other end of the plastic soft packaging bag according to the measurement. The middle of the plastic soft packaging bag is sealed and separated by a plastic clip, and then sealed with a sealing machine under nitrogen protection.

[0105] A and B are charged in a mass ratio of A∶B = 1 - 1.05∶1. See the mine gas pipeline sealing bag filled with the A and B combined materials.

[0106] The plastic soft packaging bag and the plastic clip are provided by Shanxi Synthetic Materials Industry Technology Research Institute Co., Ltd.

[0107] Third step, preparation of the polymer composite foam material for plugging the borehole:

[0108] Step 1: At room temperature, squeeze and knead the plastic soft packaging bags containing the A and B composition components by hand respectively to make the A and B components in the bags in a flowing state;

[0109] Step 2: Extract the middle plastic clip of the plastic soft packaging bag, squeeze and knead the A and B components for 30 - 60 s, and then fill the plastic soft packaging bag into the borehole. The A and B components generate the polymer composite foam material for plugging the borehole through polymerization reaction.

[0110] Example 4

[0111] For the polymer composite material for plugging the borehole in this example, before molding, it is composed of the following mass parts of A and B composition components:

[0112] Component A:

[0113] 118 parts of PAPI, 9 parts of flame retardant MCA, 3 parts of polymer foaming microspheres, 1 part of light calcium carbonate powder, 3 parts of conductive carbon black powder, 4 parts of diethylene glycol dibenzoate, 3 parts of YRFC-RG01 thixotropic agent.

[0114] Component B:

[0115] 48 parts of 4110 polyether, 48 parts of 635 polyether, 3 parts of 403 polyether, 3 parts of foam stabilizer, 14 parts of foaming agent, 9 parts of flame retardant MP, 12 parts of DMMP flame retardant, 0.9 part of composite catalyst, 3 parts of antistatic agent, 3 parts of aluminum hydroxide powder, 2 parts of YRFC-RG02A thixotropic agent.

[0116] Further preferred solution: The PAPI is polyphenyl polymethylene polyisocyanate, with the mass content of -NCO group being 31.1 - 31.5%, produced by Wanhua Chemical Group Co., Ltd.; the flame retardant MCA is white crystalline fine powder melamine cyanurate, a commercially available flame retardant with an average particle size of less than 50 microns; the polymer foamed microspheres are produced by AkzoNobel of the Netherlands, model 551DE40D42; the diethylene glycol dibenzoate is commercially available; the thixotropic agent is YRFC-RG01 and YRFC-RG02A type thixotropic agent produced by Guangzhou Yourun; the conductive carbon black powder and light calcium carbonate powder are commercially available, with an average particle size of less than 10 microns, and are dried before use.

[0117] Further preferred solution: The 4110 polyether, 635 polyether, and 403 polyether are polyether polyols produced by Hebei Yadong Chemical Group Co., Ltd.; the foam stabilizer is L-6900 type polymer rigid foam stabilizer produced by Momentive Performance Materials Inc. of the United States; the antistatic agent is Ortegol-AST type antistatic agent produced by Goldschmidt of Germany; the foaming agent model HFO-1336mzzZ is cis-hexafluorobutene, sold by fluorine chemical refrigerant distributor; the flame retardant MP is commercially available melamine phosphate with an average particle size of less than 50 microns; the DMMP flame retardant is commercially available dimethyl methylphosphonate; the aluminum hydroxide powder is commercially available with an average particle size of less than 10 microns.

[0118] The preparation method of the further composite catalyst is as follows: Dissolve 40 parts of triethylenediamine in 60 parts of diethylene glycol solvent at room temperature, and then add 4 parts of dibutyltin dilaurate solution thereto, and stir and mix evenly.

[0119] The preparation method of the polymer composite foam material for plugging boreholes in the present invention is prepared according to the following steps:

[0120] First step: Preparation of component A:

[0121] Step 1: Add 118 parts of PAPI, 9 parts of flame retardant MCA, 3 parts of polymer foamed microspheres, 1 part of light calcium carbonate powder, and 3 parts of conductive carbon black powder into a mixing container in sequence, and stir and mix evenly at room temperature under nitrogen protection, with the stirring rate being 30 - 40 r / min;

[0122] Step 2: Then add 4 parts of diethylene glycol dibenzoate and 3 parts of YRFC-RG01 thixotropic agent into the above mixed materials, and continue to stir for 20 minutes to obtain component A;

[0123] Step 3: Fill component A into one end of a plastic soft packaging bag according to the measurement, close and separate the middle part of the plastic soft packaging bag with a plastic clip, and then seal it with a sealing machine under nitrogen protection.

[0124] Step 2: Preparation of Component B:

[0125] Step 1: Add 48 parts of 4110 polyether, 48 parts of 635 polyether, and 3 parts of 403 polyether into the mixing kettle in sequence. Under the condition of a stirring rate of 30 - 40 r / min, stir evenly at normal temperature;

[0126] Step 2: Then add 3 parts of foam stabilizer, 12 parts of DMMP flame retardant, and 0.9 part of composite catalyst, and stir further evenly;

[0127] Step 3: Add 9 parts of flame retardant MP, 3 parts of antistatic agent, and 3 parts of aluminum hydroxide powder into the mixing kettle and stir evenly;

[0128] Step 4: Finally, add 2 parts of YRFC - RG02A thixotropic agent and 14 parts of foaming agent, and stir and mix evenly at normal temperature to obtain Component B;

[0129] Step 5: Fill Component B into the other end of the plastic flexible packaging bag according to the measurement. Seal and separate the middle part of the plastic flexible packaging bag with a plastic clip, and then seal it with a sealing machine under nitrogen protection.

[0130] A and B are charged in a mass ratio of A∶B = 1 - 1.05∶1. The mine gas pipeline sealing bag filled with the A and B combined materials is shown.

[0131] The plastic flexible packaging bag and the plastic clip are provided by Shanxi Synthetic Materials Industry Technology Research Institute Co., Ltd.

[0132] Step 3: Preparation of the polymer composite foam material for plugging boreholes:

[0133] Step 1: At normal temperature, squeeze and knead the plastic flexible packaging bags containing the A and B composition components by hand respectively to make the A and B components in the bags in a flowing state;

[0134] Step 2: Extract the middle plastic clip of the plastic flexible packaging bag, squeeze and knead the A and B components for 30 - 60 s, and then fill the plastic flexible packaging bag into the borehole. The A and B components generate the polymer composite foam material for plugging the borehole through polymerization reaction.

[0135] Example 5

[0136] For the polymer composite material for plugging boreholes in this example, before molding, it is composed of the following mass parts of A and B composition components:

[0137] Component A:

[0138] 116 parts of PAPI, 7 parts of flame retardant MCA, 2 parts of polymer foaming microspheres, 1 part of light calcium carbonate powder, 3 parts of conductive carbon black powder, 3 parts of diethylene glycol dibenzoate, 3 parts of thixotropic agent YRFC-RG01.

[0139] Component B:

[0140] 46 parts of polyether 4110, 48 parts of polyether 635, 2 parts of polyether 403, 2 parts of foam stabilizer, 12 parts of foaming agent, 7 parts of flame retardant MP, 11 parts of DMMP flame retardant, 0.8 part of composite catalyst, 3 parts of antistatic agent, 2 parts of aluminum hydroxide powder, 2 parts of thixotropic agent YRFC-RG02A.

[0141] In a further preferred embodiment, the PAPI is polyphenyl polymethylene polyisocyanate with a mass content of -NCO groups of 31.1 - 31.5%, produced by Wanhua Chemical Group Co., Ltd.; the flame retardant MCA is white crystalline fine powder melamine cyanurate, a commercially available flame retardant with an average particle size of less than 50 microns; the polymer foaming microspheres are produced by AkzoNobel of the Netherlands, model 551DE40D42; the diethylene glycol dibenzoate is commercially available; the thixotropic agent is YRFC-RG01 and YRFC-RG02A type thixotropic agent produced by Guangzhou Yourun; the conductive carbon black powder and the light calcium carbonate powder are commercially available, with an average particle size of less than 10 microns and are dried before use.

[0142] In a further preferred embodiment, the polyether 4110, polyether 635, and polyether 403 are polyether polyols produced by Hebei Yadong Chemical Group Co., Ltd.; the foam stabilizer is L-6900 type polyurethane rigid foam stabilizer produced by Momentive Performance Materials Inc. of the United States; the antistatic agent is Ortegol-AST type antistatic agent produced by Goldschmidt AG of Germany; the foaming agent model HFO-1336mzzZ is cis-hexafluorobutene, sold by fluorine chemical refrigerant distributors; the flame retardant MP is commercially available melamine phosphate with an average particle size of less than 50 microns; the DMMP flame retardant is commercially available dimethyl methylphosphonate; the aluminum hydroxide powder is commercially available with an average particle size of less than 10 microns.

[0143] The preparation method of the further composite catalyst is to dissolve 40 parts of triethylenediamine in 60 parts of diethylene glycol solvent at room temperature, and then add 4 parts of dibutyltin dilaurate solution and stir to mix evenly.

[0144] The preparation method of the above polymer composite foam material for plugging boreholes in the present invention is prepared according to the following steps:

[0145] First step, preparation of Component A:

[0146] Step 1: Add 116 parts of PAPI, 7 parts of flame retardant MCA, 2 parts of polymer foaming microspheres, 1 part of light calcium carbonate powder, and 3 parts of conductive carbon black powder into the mixing container in sequence, and stir and mix evenly at normal temperature under nitrogen protection. The stirring rate is 30 - 40 r / min;

[0147] Step 2: Then add 3 parts of diethylene glycol dibenzoate and 3 parts of YRFC - RG01 thixotropic agent into the above - mentioned mixed materials, and continue to stir for 20 minutes to obtain Component A;

[0148] Step 3: Fill Component A into one end of a plastic soft - packaging bag according to the measurement. The middle part of the plastic soft - packaging bag is sealed and separated by a plastic clip, and then sealed with a sealing machine under nitrogen protection.

[0149] Second step: Preparation of Component B:

[0150] Step 1: Add 46 parts of 4110 polyether, 48 parts of 635 polyether, and 2 parts of 403 polyether into the mixing kettle in sequence, and stir and mix evenly at normal temperature under the condition that the stirring rate is 30 - 40 r / min;

[0151] Step 2: Then add 2 parts of foam stabilizer, 11 parts of DMMP flame retardant, and 0.8 part of composite catalyst, and further stir and mix evenly;

[0152] Step 3: Then add 7 parts of flame retardant MP, 3 parts of antistatic agent, and 2 parts of aluminum hydroxide powder into the mixing kettle and stir evenly;

[0153] Step 4: Finally, add 2 parts of YRFC - RG02A thixotropic agent and 12 parts of foaming agent, and stir and mix evenly at normal temperature to obtain Component B;

[0154] Step 5: Fill Component B into the other end of the plastic soft - packaging bag according to the measurement. The middle part of the plastic soft - packaging bag is sealed and separated by a plastic clip, and then sealed with a sealing machine under nitrogen protection.

[0155] A and B are loaded according to the mass ratio A∶B = 1 - 1.05∶1. The mine gas pipeline sealing bag containing A and B combined materials is shown as follows.

[0156] The plastic soft - packaging bag and the plastic clip are provided by Shanxi Synthetic Materials Industry Technology Research Institute Co., Ltd.

[0157] Third step: Preparation of the polymer composite foam material for plugging boreholes:

[0158] Step 1: At normal temperature, squeeze and knead the plastic soft - packaging bags containing Component A and Component B of the composition by hand respectively to make the A and B components in the bags in a flowing state;

[0159] Step 2: Extract the middle plastic clip of the plastic soft packaging bag, knead and mix components A and B by extrusion for 30 - 60 s, and then fill the plastic soft packaging bag into the drilled hole. Through the polymerization reaction of components A and B, a polymer composite foam material for plugging the drilled hole is formed.

[0160] Referring to relevant standards and judgment rules such as GB / T 21558 - 2008 Sprayed rigid polymer foam plastics for building thermal insulation, GB / T 26689 - 2011 Polymer foam plastics for refrigerators and freezers, GB / T 10799 - 2008 Determination of open - cell and closed - cell volume percentages of rigid foam plastics, MT 113 - 1995 General test methods for flame retardancy and antistatic properties of polymer products used in coal mines, etc., the performance of the polymer composite foam material for plugging drilled holes in mines generated by the present invention is as follows:

[0161] Table 1. Performance of a polymer composite foam material for plugging drilled holes in mines

[0162]

[0163]

[0164] The polymer composite foam material for plugging the drilled hole is composed of two composition components A and B. Components A and B are respectively filled into both ends of the soft - packaging plastic bag, and the middle of the soft - packaging plastic bag is separated by a plastic clip to form a whole. During use, first knead components A and B by hand into a flowing state, then remove the plastic clip in the middle of the bag, fully mix components A and B by hand in the soft - packaging bag, and then fill them into the drilled hole to react and expand to plug the drilled hole. The polymer and polymer microspheres foam twice, with a large expansion ratio, high foam strength, and good hole - plugging effect.

Claims

1. A polymer composite foam material for plugging boreholes in mines, characterized in that: It is composed of component A composition and component B composition in parts by mass; wherein Component A: 110 - 120 parts of PAPI, 6 - 10 parts of flame retardant MCA, 1 - 3 parts of polymer foaming microspheres, 1 - 3 parts of light calcium carbonate powder, 2 - 5 parts of conductive carbon black powder, 2 - 5 parts of diethylene glycol dibenzoate, 2 - 3 parts of YRFC - RG01 thixotropic agent; Component B: 45 - 50 parts of 4110 polyether, 45 - 50 parts of 635 polyether, 1 - 3 parts of 403 polyether, 2 - 3 parts of foam stabilizer, 10 - 15 parts of foaming agent, 5 - 10 parts of flame retardant MP, 10 - 12 parts of DMMP flame retardant, 0.5 - 1.0 part of composite catalyst, 3 - 5 parts of antistatic agent, 1 - 3 parts of aluminum hydroxide powder, 2 - 3 parts of YRFC - RG02A thixotropic agent; In the component A, PAPI is polyphenyl polymethylene polyisocyanate, the mass content of -NCO group is 31.1 - 31.5%, produced by Wanhua Chemical Group Co., Ltd.; the flame retardant MCA is white crystalline fine powder melamine cyanurate, which is a commercially available flame retardant with an average particle size of less than 50 microns; the polymer foaming microspheres are produced by AkzoNobel of the Netherlands, model 551DE40D42; the diethylene glycol dibenzoate is commercially available; the thixotropic agents are YRFC - RG01 and YRFC - RG02A thixotropic agents produced by Guangzhou Yourun; the conductive carbon black powder and light calcium carbonate powder are commercially available, with an average particle size of less than 10 microns and are dried before use; In the component B, 4110 polyether, 635 polyether, and 403 polyether are polyether polyols produced by Hebei Yadong Chemical Group Co., Ltd.; the foam stabilizer is L - 6900 type polyurethane rigid foam foam stabilizer produced by Momentive Performance Materials Inc. of the United States; the antistatic agent is Ortegol - AST type antistatic agent produced by Goldschmidt of Germany; the foaming agent model HFO - 1336mzzZ is cis - hexafluorobutene; the flame retardant MP is commercially available melamine phosphate with an average particle size of less than 50 microns; the DMMP flame retardant is commercially available dimethyl methylphosphonate; the aluminum hydroxide powder, with an average particle size of less than 10 microns, is commercially available.

2. The polymer composite foam material for plugging boreholes in mines according to claim 1, characterized in that: The preparation method of the composite catalyst is as follows: At room temperature, 40 parts of triethylenediamine are dissolved in 60 parts of diethylene glycol solvent, and then 4 parts of dibutyltin dilaurate solution are added thereto, and stirred and mixed evenly.

3. The preparation method of the polymer composite foam material for plugging boreholes in mines according to any one of claims 1 to 2, characterized in that, It is prepared according to the following steps: The first step, preparation of component A: Step 1: Add 110 - 120 parts of PAPI, 6 - 10 parts of flame retardant MCA, 1 - 3 parts of polymer foaming microspheres, 1 - 3 parts of light calcium carbonate powder, and 2 - 5 parts of conductive carbon black powder into a mixing container in sequence, and stir and mix evenly at room temperature under nitrogen protection, with a stirring rate of 30 - 40 r / min; Step 2: Then add 2 - 5 parts of diethylene glycol dibenzoate and 2 - 3 parts of YRFC - RG01 thixotropic agent into the mixed material obtained in Step 1, and continue stirring for 20 minutes to obtain component A; Step 3: Then, charge Component A into one end of a plastic soft packaging bag according to the measurement. Seal off the middle of the plastic soft packaging bag with a plastic clip. Finally, seal it with a sealing machine under nitrogen protection; Second step, preparation of Component B: Step 1: Add 45 - 50 parts of 4110 polyether, 45 - 50 parts of 635 polyether, and 1 - 3 parts of 403 polyether into the mixing kettle in sequence, and stir evenly at normal temperature under the condition that the stirring rate is 30 - 40 r / min; Step 2: Then add 2 - 3 parts of foam stabilizer, 10 - 12 parts of DMMP flame retardant, and 0.5 - 1.0 part of composite catalyst, and stir evenly further; Step 3: Add 5 - 10 parts of flame retardant MP, 3 - 5 parts of antistatic agent, and 1 - 3 parts of aluminum hydroxide powder into the mixing kettle and stir evenly; Step 4: Finally, add 2 - 3 parts of YRFC - RG02A thixotropic agent and 10 - 15 parts of foaming agent, and stir and mix evenly at normal temperature to obtain Component B; Step 5: Charge Component B into the other end of the plastic soft packaging bag according to the measurement. Seal off the middle of the plastic soft packaging bag with a plastic clip, and seal it with a sealing machine under nitrogen protection; Charge A and B according to the mass ratio A∶B = 1 - 1.05∶1; Third step, preparation of polymer composite foam material for plugging boreholes: Step 1: At normal temperature, squeeze and knead the plastic soft packaging bags containing Components A and B of the composition by hand respectively to make Components A and B in the bags in a flowing state; Step 2: Extract the middle plastic clip of the plastic soft packaging bag, squeeze and knead and mix Components A and B in the plastic soft packaging bag for 30 - 60 s, and then fill the plastic soft packaging bag into the borehole. The A and B component materials generate polymer composite foam material for plugging the borehole through polymerization reaction.

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