Silicate-modified polymer grouting material for leakage plugging

Abstract

A silicate-modified polymer grouting material for leakage plugging is provided, which belongs to the technical field of silicate modification, includes 60% by weight of silicate-modified aqueous solution component, and about 40% of structural flame-retardant isocyanate. According to the proportion of the main total amount, the main components are classified into inorganic components, so the silicate-modified polymer grouting material for leakage plugging has excellent flame retardant performance, oxygen index ≥35%, adhesion ≥1.5 mPa, maximum reaction temperature ≤95° C., odor level (80° C.) ≤3.5, fog test ≤5 mg (without physical additive flame retardants diffusion to the environment). In particular, a main component of the silicate-modified aqueous solution, endows it with good surface resistance.

Claims

1. A silicate-modified polymer material for leakage plugging, comprising: prepolymerized isocyanate and silicate modified aqueous solution with a mass ratio at a range of 1:(1.2-1.4), wherein the prepolymerized isocyanate is a prepolymer obtained by the polymerization of trimethylol phosphine oxide and TDI, and has a chemical structural formula as follows: ##STR00005##

2. The silicate-modified polymer material for leakage plugging, as recited in claim 1, wherein P content of the prepolymerized isocyanate is 4.7%, N content of the prepolymerized isocyanate is 12.7%, and NCO % content of the prepolymerized isocyanate is 19%.

3. The silicate-modified polymer material for leakage plugging, as recited in claim 1, wherein the silicate-modified aqueous solution comprises: liquid sodium silicate, water, and a catalyst; wherein the liquid sodium silicate accounts for 82-87% of the silicate-modified aqueous solution by weight, and the water accounts for 12-15% by weight of the silicate-modified aqueous solution, and the catalyst accounts for 1.5-2.5% by weight of the silicate-modified aqueous solution.

4. The silicate-modified polymer material for leakage plugging, as recited in claim 3, wherein the liquid sodium silicate is an aqueous solution of sodium silicate, and a Baume degree thereof is 40.

5. The silicate-modified polymer material for leakage plugging, as recited in claim 4, wherein the liquid sodium silicate adopts 2451 by Qingdao Gulf Chemical

6. The silicate-modified polymer material for leakage plugging, as recited in claim 3, wherein the catalyst is a diethylene glycol solution of triethylenediamine with a concentration of 33%.

7. The silicate-modified polymer material for leakage plugging, as recited in claim 3, wherein the catalyst adopts 33lv by Evonik Chemistry.

8. A method for synthesizing the silicate-modified polymer material for leakage plugging, as recited in claim 1, comprising: a step of mixing pre-polyisocyanate and silicate modified aqueous solution, wherein the pre-polyisocyanate is obtained by polymerizing hydroxymethyl phosphine oxide and TDI, and a reaction equation is: ##STR00006##

9. The method for synthesizing the silicate-modified polymer material for leakage plugging, as recited in claim 8, wherein a specific synthesis process comprises steps of: (1) heating a reaction kettle to 48° C.-52° C.; (2) firstly adding all TDI, and then adding all trimethylol oxidized phosphine according to trimethylol phosphine oxide (purchased from Hubei Xingfa Chemical Group Co., Ltd.): TDI=1:(4-8) molar ratio; (3) heating the reaction kettle to 78° C.-82° C., and then reacting for 1.9 h-2.2 h; (4) by a thin film evaporator, removing excess TDI that has not reacted; (5) then cooling the reaction kettle to 48° C.-52° C., taking out from the kettle and packaging to obtain pre-polyisocyanate with P content of 4.7%, N content of 12.7%, and NCO % content of 19%; (6) mixing the pre-polyisocyanate and the silicate-modified aqueous solution according to a mass ratio (1.2-1.4):1 to obtain the silicate-modified polymer material for leakage plugging.

Description

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

[0043] The technical solutions in the examples of the present invention will be clearly and completely described below. Obviously, the examples described are only a part of the examples of the present invention, rather than all the examples. Based on the examples in the present invention, all other examples obtained by those of ordinary skill in the art without creative work are within the protection scope of the present invention.

Example 1

[0044] A specific example of the applying pre-polyisocyanate compound in this Example to the silicate-modified polymer material for leakage plugging is as follows.

[0045] (1) The formula of silicate aqueous solution is as follows:

TABLE-US-00001 2451 (Aqueous silicate solution, Qingdao Bay) 85 Water 13 A33 (Catalyst, Evonik Specialty Chemicals (Shanghai) Co., Ltd.) 2 Total 100

[0046] (2) (2) Pre-polymerized isocyanate A:

[0047] Pre-polymerized isocyanate A is obtained by polymerizing trimethylol phosphine oxide and TDI to obtain a prepolymer; wherein P content is 4.7%, N content is 12.7%, and NCO % content is 19%. A chemical structure of the pre-polymerized isocyanate A is as follows:

##STR00003##

[0048] Prepolymerized isocyanate A is obtained by polymerizing trimethylol phosphine oxide and TDI, wherein a reaction equation is as follows:

##STR00004##

[0049] A specific synthesis process comprises steps of:

[0050] (1) heating a reaction kettle to 50° C.;

[0051] (2) firstly adding 1000 g of TDI, and then adding 160 g of trimethylol oxidized phosphine with a uniform speed according to trimethylol phosphine oxide (purchased from Hubei Xingfa Chemical Group Co., Ltd.): TDI=1:5 molar ratio;

[0052] (3) heating the reaction kettle to 80° C., and then reacting for 2 h;

[0053] (4) by a thin film evaporator, removing excess TDI that has not reacted;

[0054] (5) then cooling the reaction kettle to 50° C., taking out from the kettle and packaging to obtain pre-polyisocyanate with P content of 4.7%, N content of 12.7%, and NCO % content of 19%;

[0055] 130 parts of the above-mentioned silicate aqueous solution and 100 parts of the isocyanate component of each examples in the following table are mixed and stirred to prepare the silicate modified polymer material for leakage plugging in the Examples.

Examples 1-6

[0056] In the following table, E 1—Example 1; E2—Example 1; E3—Example 3; E4—Example 4; E5—Example 5; E6—Example 6

TABLE-US-00002 Component Name E 1 E 2 E 3 E 4 E 5 E 6 Isocyanate Prepolymerized Isocyanate A 100 0 0 0 0 0 WANNATE ® PM-200 0 100 0 0 100 100 Wanhua Chemical Group Co., Ltd. WANNATE ® CDMDI-100L 0 0 100 0 0 0 Wanhua Chemical Group Co., Ltd. WANNATE ® 8312 0 0 0 100 0 0 TEP 0 0 0 0 38 0 TCPP 0 0 0 0 0 98

[0057] Note: WANNATE® 8312 is a pre-polymer of DL2000 and MDI, with a viscosity (25° C.) of 550-800 mPas, a NOC % at a range of 15.0-16.0%, and is a colorless or light yellow transparent liquid at room temperature.

[0058] WANNATE® CDMDI-100L is liquefied MDI.

[0059] WANNATE® PM-200 is a polymethylene polyphenyl polyisocyanate.

[0060] The isocyanates in the above examples 1, 2, 3, 4, 5, and 6 according to the formula fractions in the above table are equivalent in weight, and fully reacted with the silicate aqueous solution by a weight ratio of 100:130.

TABLE-US-00003 Example Example Example Example Example Example Item 1 2 3 4 5 6 Flame Oxygen Index 37.2 29.5 30.5 29.3 35.0 36.0 retardant properties Physical Density kg/m.sup.3 165 160 155 162 159 159 properties Adhesion 1.58 1.21 1.10 1.53 1.18 1.08 Maximum 91 120 115 98 105 103 reaction temperature/° C. elongation at 35% 15% 17% 31% 10% 9% break/% Environmental Fog test 3.9 5.8 5.9 3.9 49 69 performance Odor rating 3.5 4.0 4.0 3.5 4.5 4.5 (80° C.) Halogen content 0 0 0 0 0 17% Smoke Toxicity 3.7 4.0 4.2 3.9 5.7 6.8 Index

[0061] The flame retardant and physical properties of each example are as follows:

[0062] Flame Retardant Properties and Physical Properties Test Standard: AQ1089-2020

[0063] Odor level test standard: VDA270: 1992,

[0064] Fog test test standard: Q/ZK JS 364-201903

[0065] On the basis of Example 1, Example 2 utilizes WANNATE® PM-200 of the same quality instead of modified Isocyanate A, everything else remained unchanged, the oxygen index was reduced from 37.2 to 29.5, and the flame retardant performance was reduced; the adhesion was reduced from 1.58 to 1.21 MPa, the bond strength decreased; the maximum reaction temperature increased from 91° C. to 120° C., the maximum reaction temperature increased significantly; the elongation at break decreased from 35% to 15%, the flexibility decreased; the fog test increased from 3.9 to 5.8, the odor level From 3.5 to 4.0, the flue gas toxicity index increased from 3.7 to 4.0, and the environmental protection performance decreased. To sum up, it shows that compared with WANNATE® PM-200, modified isocyanate can endow silicate modified polymer materials for leakage plugging with better flame retardant performance and environmental protection performance, lower maximum reaction temperature, and better performance. toughness and bond strength.

[0066] Example 3 is on the basis of Example 1, WANNATE® CDMDI-100L of the same quality was used instead of modified isocyanate. Everything else remained unchanged. The oxygen index was reduced from 37.2 to 30.5, indicating that the flame retardancy decreased; the adhesion was reduced from 1.58 to 1.10 MPa., the bond strength decreased; the maximum reaction temperature increased from 91° C. to 115° C., and the maximum reaction temperature increased significantly; the elongation at break decreased from 35% to 17%, and the flexibility decreased; the fog test increased from 3.9 to 5.9, and the odor level increased from 3.9 to 5.9. From 3.5 to 4.0, the flue gas toxicity index rose from 3.7 to 4.2, and the environmental performance decreased. To sum up, it shows that compared with WANNATE® CDMDI-100L, modified isocyanate can endow the silicate modified polymer material for leakage plugging with better flame retardant performance and environmental protection performance, lower maximum reaction temperature, and better performance of toughness and bond strength.

[0067] Example 4 is on the basis of Example 1 and uses WANNATE® 8312 of the same quality to replace the modified isocyanate, everything else remains unchanged, the elongation at break is reduced from 35% to 31%, the flexibility is only slightly decreased, but the oxygen index is from 37.2 It can be reduced to 29.3, which means that under the same toughness, the modified isocyanate A can give the material better flame retardant properties; the adhesion force is reduced from 1.58 to 1.53 MPa, and the bond strength is only slightly decreased; the maximum reaction temperature increased from 91° C. to 98° C., the maximum reaction temperature increased significantly; the fog test did not change, the odor level did not change, the smoke toxicity index rose from 3.7 to 3.9, and the environmental performance was comparable. To sum up, it is shown that the modified isocyanate has the same toughness and environmental protection performance compared with WANNATE® 8312, but it can endow the silicate modified polymer material for leakage plugging with better flame retardant performance.

[0068] Example 5 is on the basis of Example 1, PM200 and flame retardant TEP are used to replace modified isocyanate A. The phosphorus content in the isocyanate component is 4.7%, which is the same as modified isocyanate A, and everything else remains unchanged. The adhesion is from 1.58 Reduced to 1.18 MPa, the bond strength decreased; the maximum reaction temperature increased from 91° C. to 105° C., the maximum reaction temperature increased significantly; the elongation at break decreased from 35% to 10%, the flexibility decreased greatly; the fog test increased from 3.9 to 49, the odor level has risen from 3.5 to 4.5, the smoke toxicity index has risen from 3.7 to 5.7, and the environmental performance has dropped significantly. To sum up, it shows that compared with PM200 and flame retardant TEP, the modified isocyanate can endow the silicate modified polymer material for leakage plugging with better environmental performance and lower maximum response temperature and better toughness and bond strength when the phosphorus content is the same.

[0069] Example 6 is on the basis of Example 1, PM200 and flame retardant Tcpp are used to replace modified isocyanate A. The phosphorus content in the isocyanate component is 4.7%, which is consistent with modified isocyanate A, and everything else remains unchanged. The adhesion is from 1.58 Reduced to 1.08 MPa, the bond strength decreased; the maximum reaction temperature increased from 91° C. to 103° C., and the maximum reaction temperature increased significantly; the elongation at break decreased from 35% to 9%, and the flexibility decreased significantly; the fog test increased from 3.9 to 69, the odor level has risen from 3.5 to 4.5, the smoke toxicity index has risen from 3.7 to 6.8, and the environmental performance has dropped significantly. To sum up, it shows that compared with PM200 and flame retardant TCPP, the modified isocyanate can endow the silicate modified polymer material for leakage plugging with better environmental performance and lower maximum response temperature, better toughness and bond strength when the phosphorus content is the same.

Example 7

[0070] The cement polymer mortar mixed aggregate spray coating commonly used in coal mines was selected for testing, and the test results are shown in the following table.

TABLE-US-00004 Items Example 1 Example 7 Curing time 1 min 2 h Density kg/m.sup.3 165 No foaming Adhesion 1.58 0.8 Maximum reaction 91 — temperature/° C. Elongation at break, % 35% 5% Fog test 3.9 6.0 Odor rating (80° C.) 3.5 4.2 Smoke Toxicity Index 3.7 3.8 Whether there is dusty No Heavy dusting when powder and emulsion are mixed Whether there is sagging No Easy to sag when the powder content is small Whether there No Small cracks are easy to exist are small cracks when the powder content is high Whether there is a No Yes local cracking problem Whether there is No Yes a shedding problem

[0071] From the comparison between Example 7 and Example 1, the silicate-modified polymer material for leakage plugging explained in the present invention does not have the problems of local cracking and falling off, as well as springback and dust, which are commonly used in coal mines. Exceeding the standard, sagging phenomenon; fast curing time, can be cured and put into use within 1 min, the elongation at break after curing reaches 35%, far exceeding the elongation of ordinary concrete by 5%, and the bond strength is 1.58 MPa, which is better than that commonly used in coal mines. Cement polymer mortar mixed with aggregate spray coating 0.8 MPa. To sum up, the silicate-modified polymer material for leakage plugging described in the present invention is much better than the cement-polymer-mortar mixed aggregate spray coating commonly used in coal mines in adhesion, flexibility, curing time, and environmental protection performance.

Example 8

[0072] The formula and properties of conventional polyurethane materials are shown in the following table:

[0073] The recipe is shown in the table below:

TABLE-US-00005 Mass Mass No. Component A fraction Component B fraction 1 Polyether 8630 40 WANNATE ®PM-200, 100 2 Polyether 2305 25 3 TCPP 25 4 Water 0.5 5 141b 7.5 6 Potassium acetate 2 7 Total 100 Total 100

[0074] The performance data comparison is shown in the following table:

TABLE-US-00006 Data in Data in No. Performance Example 8 Example 1 1 Oxygen Index 29 35.2 2 Density kg/m.sup.3 45 165 3 adhesion 0.9 1.58 4 Maximum reaction temperature/° C. 120 91 5 Odor rating (80° C.) 4.0 3.5 6 Fog test 53 3.9 7 Halogen content 3.86% 0 10 Elongation at break (%)   15% 35% 11 Surface resistance (Ω) 3.5 × 10.sup.9 1.5 × 10.sup.5

[0075] Comparing the data of Example 8 and Example 1, it can be found that when the oxygen index of the traditional organic polyurethane material reaches 29, the maximum reaction temperature is 120° C., which exceeds the maximum reaction temperature of Example 1 of 91° C., which increases the application in coal mines. Potential safety hazards; Example 8 odor level (80° C.), 4.0, fog test 53, Example 1 odor level 3.5, fog test 3.9, Example 1 has better environmental performance; Example 8 halogen content 3.86%, when burning It will release corrosive or irritating hydrogen halide gas, produce poisonous carcinogens polybrominated benzoxins and polybrominated dibenzofurans, and increase the halogen content in coal. The surface resistance of Example 8 reached 1.5×109Ω, far exceeding the surface resistance of Example 1, which was 3.7×105Ω. The elongation at break of Example 8 was 15%, the elongation at break of 1 was 35%, and the toughness of Example 1 was better. Excellent, in summary, the silicate-modified polymer material for leakage plugging described in the present invention has better environmental protection performance and toughness, lower surface conductivity and better safety performance than traditional organic polyurethane materials.

[0076] One skilled in the art will understand that the embodiment of the present invention as shown in the drawings and described above is exemplary only and not intended to be limiting.

[0077] It will thus be seen that the objects of the present invention have been fully and effectively accomplished. Its embodiments have been shown and described for the purposes of illustrating the functional and structural principles of the present invention and is subject to change without departure from such principles. Therefore, this invention includes all modifications encompassed within the spirit and scope of the following claims.