Phenolic resin modified polyurethane grouting reinforcement material for coal mine and preparation method of phenolic resin modified polyurethane grouting reinforcement material

Abstract

The phenolic resin is used for modifying the polyurethane reinforced grouting material for the coal mine, so that the reaction temperature of a system is reduced, and the flame retardant property of the material is improved. The phenolic resin modified polyurethane grouting reinforcement material for the coal mine is composed of a component A and a component B. Phenolic resin is introduced into a polyurethane grouting reinforcement system, and phenolic hydroxyl groups in the phenolic resin are used for replacing part of hydroxyl groups in polyether polyol to react with-NCO, so that the purpose of reducing reaction heat is achieved; meanwhile, a large number of benzene ring structures are introduced into the phenolic resin, so that the flame retardant property of the grouting material can be improved to a certain extent.

Description

TECHNICAL FIELD

[0003] The present application belongs to the field of new materials, and particularly relates to a phenolic resin modified polyurethane grouting material for coal mines and a preparation method thereof. BACKGROUND

[0004] In the process of coal mine production, roof fall and rib spalling accidents of broken coal and rock mass are prone to occur in the working face due to geological reasons, which seriously threatens the safety of underground production in coal mines. In order to prevent such accidents, it is necessary to use grouting materials to reinforce the broken coal and rock mass. Traditional grouting materials mainly include cement-based grouting materials. Due to the long solidification time and poor permeability of the cement-based grouting materials, they cannot meet the current needs of safety production in coal mines, and are gradually replaced by chemical grouting materials. The chemical grouting materials currently used are mainly polyurethane materials. Although the polyurethane materials have the advantages of adjustable solidification speed and good mechanical properties, they have the disadvantages of poor flame retardancy, large reaction heat and high reaction temperature (the internal maximum reaction temperature can reach 160℃), which may cause smoke or even fire in specific environments (especially in high-gas mines).

[0005] Phenolic resin is a material with excellent flame retardancy (oxygen index greater than 38%) and low reaction temperature during solidification. In the present application, phenolic resin is used to modify the mechanical properties of polyurethane grouting materials, so as to reduce the reaction temperature of the system and improve the flame retardancy of the materials while ensuring the excellent mechanical properties of the polyurethane materials. SUMMARY

[0006] The present application provides a phenolic resin modified polyurethane grouting material for coal mines and a preparation method thereof. The principle is to introduce phenolic resin (the specific structure is shown in Figure 1 ) into the polyurethane grouting system, and use the phenolic hydroxyl groups in the phenolic resin to replace part of the hydroxyl groups in the polyether polyol to react with -NCO, so as to reduce the reaction heat. At the same time, the introduction of a large number of benzene ring structures in the phenolic resin can improve the flame retardancy of the grouting material to a certain extent.

[0007] The phenolic resin modified polyurethane grouting material for coal mines according to the present application is characterized in that the material is composed of two components A and B. Component A is composed of phenolic resin, polyether polyol, flame retardant and catalyst, and is used as the main resin; component B is composed of polymeric MDI, plasticizer and flame retardant, and is mainly used as the curing agent of component A. When used, the volume ratio of component A to component B is 1:1, and component A is composed of the following substances in mass fraction:

[0008]

[0009] The aldehyde compound is one or more of 37% formaldehyde solution, glutaraldehyde, and polyformaldehyde.

[0010] The basic catalyst is one or more of triethanolamine, diethanolamine, and triethylamine.

[0011] The polyether polyol A is a polyether polyol with a functionality of 2-4 and a molecular weight of 100-1000, preferably MN-500 produced by Shandong Lansheng Dongda Chemical Co., Ltd.

[0012] The flame retardant is one or more of TCPP, TCEP, DMMP, and DEEP.

[0013] The preparation method of the phenolic resin modified polyurethane grouting reinforcement material A component for coal mines according to the present application comprises the following steps:

[0014] 1) The formula amount of aldehyde compound, phenol, and basic catalyst is weighed and stirred at 70-80°C for 1.5-3h.

[0015] 2) After step 1 is completed, the formula amount of polyether polyol and flame retardant is added, and after being stirred uniformly, vacuum dehydration is performed at 70-80°C until the moisture content is <0.05% and the free formaldehyde content is <0.2%.

[0016] 3) After step 2 is completed, the above product is cooled to below 35°C, dibutyltin dilaurate is added, and stirring is performed uniformly, thereby obtaining the phenolic resin modified polyurethane grouting reinforcement material A component for coal mines according to the present application.

[0017] The phenolic resin modified polyurethane grouting reinforcement material B component for coal mines according to the present application is composed of the following substances in mass fraction:

[0018] Polymeric MDI 50-70 parts

[0019] Plasticizer 10-30 parts

[0020] Flame retardant 10-30 parts

[0021] The polymeric MDI is preferably M20S provided by Shanghai BASF Polyurethane Co., Ltd.

[0022] The plasticizer is one or more of dibutyl phthalate (DBP), dioctyl phthalate (DOP), and chlorinated paraffin.

[0023] The flame retardant is one or more of TCPP, TCEP, DMMP, and DEEP.

[0024] The preparation method of the phenolic resin modified coal mine polyurethane grouting reinforcing material B component is as follows: the formula amount of polymeric MDI, plasticizer and flame retardant are mixed and stirred uniformly at normal temperature to obtain the product.

[0025] The A and B components are mixed uniformly at a volume ratio of A:B=1:1, and then the reaction and curing are started, and the phenolic resin modified coal mine polyurethane grouting reinforcing material is obtained after the curing is completed. Specific implementation method Example: One,

[0027] The 37% formaldehyde aqueous solution 115g, phenol 98g, triethanolamine 0.3g are weighed and stirred to react at 75°C for 2h, then the polyether polyol 50g, TCPP 26g are added and stirred uniformly, and then vacuum dehydration is carried out at 75°C until the water content is <0.05% and the free formaldehyde content is <0.2%, and then the obtained product is cooled to below 35°C, and then dibutyltin dilaurate 1.8g is added and stirred uniformly to obtain the A component; the polymeric MDI 65g, DBP 10g and TCPP 25g are weighed and mixed uniformly to obtain the B component.

[0028] The A and B components are mixed uniformly at a volume ratio of A:B=1:1, and then the reaction and curing are started, and the phenolic resin modified coal mine polyurethane grouting reinforcing material is obtained after the curing is completed.

[0029] Two,

[0031] The 37% formaldehyde aqueous solution 115g, phenol 98g, triethanolamine 0.3g are weighed and stirred to react at 75°C for 2h, then the polyether polyol 50g, TCPP 26g are added and stirred uniformly, and then vacuum dehydration is carried out at 75°C until the water content is <0.05% and the free formaldehyde content is <0.2%, and then the obtained product is cooled to below 35°C, and then dibutyltin dilaurate 1.8g is added and stirred uniformly to obtain the A component; the polymeric MDI 65g, DBP 10g and TCPP 25g are weighed and mixed uniformly to obtain the B component.

[0032] The A and B components are mixed uniformly at a volume ratio of A:B=1:1, and then the reaction and curing are started, and the phenolic resin modified coal mine polyurethane grouting reinforcing material is obtained after the curing is completed.

[0033] Two,

[0031] The 37% formaldehyde aqueous solution 115g, phenol 98g, triethanolamine 0.3g are weighed and stirred to react at 75°C for 2h, then the polyether polyol 50g, TCPP 26g are added and stirred uniformly, and then vacuum dehydration is carried out at 75°C until the water content is <0.05% and the free formaldehyde content is <0.2%, and then the obtained product is cooled to below 35°C, and then dibutyltin dilaurate 1.8g is added and stirred uniformly to obtain the A component; the polymeric MDI 65g, DBP 10g and TCPP 25g are weighed and mixed uniformly to obtain the B component.

[0034] III.,

[0036] Take 37% formaldehyde solution 100 g, glutaraldehyde 22 g, phenol 96 g, triethanolamine 0.3 g in 75 ℃ under stirring reaction 2 h, then add polyether polyol 55 g, TCPP 20 g stirring uniform in 75 ℃ under vacuum dehydration, until the moisture content <0.05%, free formaldehyde content <0.2%, the product obtained cooling to 35 ℃ below the addition of dibutyltin dilaurate 2.0 g after stirring uniform, namely A component; Take polymeric MDI 70 g, DBP 10 g, TCPP 20 g mixed evenly, namely B component.

[0037] The A, B parts are mixed uniformly according to the volume ratio of A:B = 1:1, and the phenolic resin modified coal mine polyurethane grouting reinforcement material is obtained by reaction. The detection performance is as follows:

[0038] BRIEF DESCRIPTION OF DRAWINGS

[0039] Figure 1 It is a schematic diagram of phenolic resin structure, which can reflect the position of phenolic hydroxyl group and the feasibility of reaction with isocyanate.

Claims

1. The phenolic resin modified polyurethane grouting material for coal mine reinforcement according to the present application, characterized in that The material is composed of two components A and B, and the volume ratio of A component to B component is 1:1 when used.

2. The phenolic resin modified polyurethane grouting and reinforcing material for coal mine of claim 1, wherein the A component is composed of the following substances in mass fraction.

3. Aldehyde compound 80~120 parts Phenol 90~110 parts Basic catalyst 0.1~2 parts Dibutyltin dilaurate 0.2~4 parts Polyether polyol 20~60 parts Flame retardant 10~40 parts.

4. The aldehyde compound of claim 2 is one or more of 37% formaldehyde solution, glutaraldehyde, and polyformaldehyde.

5. The basic catalyst of claim 2 is one or more of triethanolamine, diethanolamine, and triethylamine.

6. The preparation method of the A component of the phenolic resin modified polyurethane grouting and reinforcing material for coal mine of claim 2, comprising the following steps.

7. 1) Weigh the formula amount of aldehyde compound, phenol, and basic catalyst, and stir and react at 70~80℃ for 1.5~3h.

8. 2) After step 1 is completed, add the formula amount of polyether polyol and flame retardant, stir until uniform, and then dehydrate under vacuum at 70~80℃ until the moisture content is <0.05% and the free formaldehyde content is <0.2%.

9. 3) After step 2 is completed, cool the above product to below 35℃, add dibutyltin dilaurate, and stir until uniform, thereby obtaining the A component of the phenolic resin modified polyurethane grouting and reinforcing material for coal mine of the present application.

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