Low-reaction thermal reinforcement material for mines and preparation method thereof

Abstract

The present invention belongs to the technical field of polyurethane, and specifically relates to a low-reaction heat mining reinforcement material and a preparation method thereof. It comprises component A and component B; component A comprises: polyether polyol A, polyether polyol B, flame retardant and catalyst; the polyether polyol A uses bisphenol compounds and sorbitol as mixed initiators; the polyether polyol B uses sucrose and sorbitol as mixed initiators; component B comprises: prepolymer, flame retardant and viscosity reducer; the prepolymer is prepared by prepolymerization of polymerized MDI and polyether polyol C; the polyether polyol C uses tetrabromobisphenol A and diol as mixed initiators. By mixing bisphenol compound polyether polyol A with a specific initiator and high-functionality polyether polyol B, the reaction heat is reduced and the strength of the reinforcement material is improved; at the same time, the polyether polyol C started with tetrabromobisphenol A enhances the flame retardancy, toughness and strength of the prepolymer; the obtained reinforcement material has high compressive strength and low reaction heat.

Description

Technical Field

[0001] The invention belongs to the technical field of polyurethane, and in particular relates to a low-reaction thermal reinforcement material for mining and a preparation method thereof. Background Art

[0002] Polyurethane materials play an important role in coal mine reinforcement. Polyurethane is a material with excellent bonding and compressive properties, which can effectively enhance the compressive strength and stability of coal rock. In the process of coal mine reinforcement, polyurethane materials are often used to fill and cement coal rock cracks and cavities, reinforce the coal body, and thus improve its compressive performance. At the same time, polyurethane can also form a solid protective layer to effectively prevent rock cracking and collapse, significantly reducing the probability of coal mine accidents.

[0003] However, as coal mining advances to a deeper level, existing organic polymer grouting materials represented by polyurethane face many challenges. They are difficult to adapt to the complex rock mass environment with high ground stress, high ground temperature, and high karst water pressure underground, and cannot effectively deal with rock mass engineering problems such as strong rheology, strong humidity and heat, and strong dynamic disasters. In particular, polyurethane grouting materials will release a large amount of heat during the curing process, resulting in excessively high reaction temperatures and accompanied by defects such as poor mechanical properties. Therefore, it is particularly important to develop a mining reinforcement material with low reaction heat and high mechanical properties. Summary of the invention

[0004] In view of the deficiencies in the prior art, the purpose of the present invention is to provide a low-reaction heat mining reinforcement material. By mixing a bisphenol compound polyether polyol A with a specific initiator and a high-functionality polyether polyol B, the reaction heat is reduced while ensuring the strength of the reinforcement material. At the same time, the polyether polyol C started with tetrabromobisphenol A enhances the flame retardancy, toughness and strength of the prepolymer. The prepared reinforcement material has high compressive strength and low reaction heat, meets mining needs and improves construction safety.

[0005] Another object of the present invention is to provide a method for preparing a low-reaction thermal reinforcement material for mining, which is scientific, reasonable, simple and easy to implement.

[0006] The technical solution adopted by the present invention is as follows:

[0007] The low-reaction thermal mineral reinforcement material comprises component A and component B in a mass ratio of 1:1.05;

[0008] The A component includes the following raw materials in parts by weight:

[0009] Polyether polyol A: 70-75 parts;

[0010] Polyether polyol B: 15-20 parts;

[0011] Flame retardant: 10 parts;

[0012] Catalyst: 0.5-0.6 parts;

[0013] Wherein, the polyether polyol A uses bisphenol compounds and sorbitol as mixed initiators, has a functionality of 3, and a hydroxyl value of 305-315 mgKOH / g;

[0014] The polyether polyol B uses sucrose and sorbitol as mixed initiators, has a functionality of 7, and a hydroxyl value of 140-180 mgKOH / g; preferably, it is INOVOL R3003 produced by Shandong INOVOL New Materials Co., Ltd.

[0015] The B component includes the following raw materials in parts by weight:

[0016] Prepolymer: 75-80 parts;

[0017] Flame retardant: 13-20 parts;

[0018] Viscosity reducer: 5-7 parts;

[0019] The prepolymer is prepared by addition polymerization of polymerized MDI and polyether polyol C; the polyether polyol C uses tetrabromobisphenol A and diol as mixed initiators, and has a hydroxyl value of 102-122 mgKOH / g; preferably, INOVOL C210FR produced by Shandong INOVOL New Materials Co., Ltd.

[0020] The polyether polyol A is prepared by using a bisphenol compound and sorbitol as mixed initiators, catalyzing the ring-opening polymerization of alkylene oxide under the action of an alkaline catalyst, and has a viscosity of 1900-2700 mPa·s; wherein the mass ratio of the bisphenol compound to sorbitol is (3-4.5):1; the mass ratio of alkylene oxide to initiator is (1-2):1; and the amount of the alkaline catalyst added is (0.9-1.2) wt.% of the total amount of the initiator and the alkylene oxide.

[0021] The bisphenol compound is one of bisphenol A, bisphenol S or bisphenol F; the alkaline catalyst is dodeca-tertiary amine or triethylamine.

[0022] The viscosity of the polyether polyol B is 700-1500 mPa·s.

[0023] The viscosity of the polyether polyol C is 800-2000 mPa·s.

[0024] The flame retardant is one of TCPP, TCEP or TEP.

[0025] The catalyst is a mixture of potassium acetate and dibutyltin dilaurate, and the mixing mass ratio is (4-5):1.

[0026] The prepolymer is prepared by reacting polymerized MDI and polyether polyol C in a mass ratio of 100:(34-37) at 60-70° C. for 2-3 hours.

[0027] The polymeric MDI is preferably one of PM200 of Wanhua Chemical Group Co., Ltd., 44V20 of Covestro AG, Germany, or M20S of BASF AG, Germany.

[0028] The viscosity reducing agent is propylene carbonate.

[0029] The method for preparing the low-reaction thermal mineral reinforcement material comprises the following steps:

[0030] (1) Put polyether polyol A, polyether polyol B, flame retardant and catalyst into a stirred tank and stir at room temperature for 1-2 hours to obtain component A;

[0031] (2) Add the prepolymer, flame retardant and viscosity reducer into a stirring kettle and stir at room temperature for 1-2 hours to obtain component B;

[0032] (3) Mix component A and component B in a mass ratio of 1:1.05 and pour into a mold. Curing at room temperature and opening the mold will give a low-reaction thermal reinforcement material.

[0033] When in use, component A and component B are mixed according to the mass ratio, and then injected into the cracks and cavities of the coal rock mass that needs to be reinforced with a grouting pump for solidification.

[0034] Compared with the prior art, the present invention has the following beneficial effects:

[0035] (1) In the component A of the present invention, the polyether polyol A containing a bisphenol compound as an initiator and the high-functionality polyether polyol B are used. After mixing, the hydroxyl value of the polyether polyol is low, which effectively reduces the heat release during the reaction process while ensuring the overall strength of the reinforcement material;

[0036] (2) In the component B of the present invention, the polyether polyol C containing tetrabromobisphenol A as an initiator is used, which not only gives the prepolymer excellent flame retardant properties, but also improves the toughness and strength of the material through the interaction between the bromine atoms in its molecules and the polymer chain, meets the strict requirements of mining reinforcement materials on strength and flame retardancy, and ensures the stability of the material in complex environments;

[0037] (3) The reaction heat of the low-reaction-heat mining reinforcement material prepared by the present invention is below 92°C, while the compressive strength is above 58MPa and the oxygen index is above 28; the low reaction heat of the system not only reduces the heat accumulation during the construction process, but also reduces the safety hazards caused by high temperature, thereby improving the safety during the construction process. DETAILED DESCRIPTION

[0038] The present invention is further described below with reference to the embodiments, but they do not limit the implementation of the present invention.

[0039] The raw materials used in the examples and comparative examples are conventional commercially available raw materials unless otherwise specified, and the process methods used in the examples and comparative examples are conventional methods in the art unless otherwise specified.

[0040] Some of the raw materials used in the examples and comparative examples are described as follows:

[0041] INOVOL R3003, purchased from Shandong INOVOL New Materials Co., Ltd. (functionality 7, initiators are sucrose and sorbitol, hydroxyl value is 140-180 mgKOH / g);

[0042] INOVOL C210FR, purchased from Shandong Yinuowei New Materials Co., Ltd. (functionality 2, initiators are tetrabromobisphenol A and propylene glycol, hydroxyl value is 102-122 mgKOH / g);

[0043] INOVOL C305, purchased from Shandong Yinuowei New Materials Co., Ltd. (functionality 3, initiator is glycerol, hydroxyl value is 340 mgKOH / g);

[0044] INOVOL C210 was purchased from Shandong INOVOL New Materials Co., Ltd. (functionality 2, initiator is propylene glycol, hydroxyl value is 107-116 mgKOH / g).

[0045] Example 1

[0046] The low-reaction thermal mineral reinforcement material comprises component A and component B in a mass ratio of 1:1.05;

[0047] The A component includes the following raw materials in parts by weight:

[0048] Polyether polyol A: 75 parts;

[0049] INOVOL R3003: 15 parts;

[0050] TCEP: 10 parts;

[0051] Catalyst: 0.6 parts;

[0052] The preparation method of the polyether polyol A is as follows: 228g of bisphenol A and 85.7g of liquid sorbitol (content 70wt.%) are put into a reactor, and 7g of triethylamine is added at the same time. After the reactor is closed for leak testing and replacement, the temperature is raised to 110±5°C under a nitrogen atmosphere, and vacuum bubbling is performed for dehydration for 1.5h; after dehydration, the temperature is lowered to 87.5±2.5°C, 90g of propylene oxide is added dropwise, and the pressure of the reactor is controlled below 0.35MPa during the addition process. After the addition is completed, the temperature is raised to 120±5°C, and the remaining 220g of propylene oxide is added dropwise, and the pressure of the reactor is controlled below 0.35Mpa during the addition process. After the addition is completed, the pressure of the reactor is maintained at 0.3±0.1Mpa, and the internal pressure is 2h. After the internal pressure is completed, the temperature is lowered to 100°C for nitrogen bubbling to remove residual small molecules. After bubbling for 1 hour, the temperature was lowered and the material was discharged to obtain polyether polyol A with a hydroxyl value of 309 mgKOH / g and a viscosity of 2234 mPa·s.

[0053] The catalyst is a mixture of potassium acetate and dibutyltin dilaurate in a mass ratio of 4:1;

[0054] The B component includes the following raw materials in parts by weight:

[0055] Prepolymer: 80 parts;

[0056] TCEP: 15 parts;

[0057] Propylene carbonate: 5 parts;

[0058] The prepolymer is prepared by reacting PM200 and INOVOL C210FR at a mass ratio of 100:34 at 60° C. for 3 hours.

[0059] The method for preparing the low-reaction thermal mineral reinforcement material comprises the following steps:

[0060] (1) Polyether polyol A, INOVOL R3003, TCEP and catalyst were placed in a stirred tank and stirred at room temperature for 2 hours to obtain component A with a viscosity of 435 mPa·s;

[0061] (2) The prepolymer, TCEP and propylene carbonate were placed in a stirred tank and stirred at room temperature for 2 h to obtain component B with a viscosity of 512 mPa·s;

[0062] (3) Mix component A and component B in a mass ratio of 1:1.05 and pour into a mold. After curing at room temperature for 8 minutes, open the mold to obtain a low-reaction thermal reinforcement material for minerals with an expansion multiple of 1.

[0063] Example 2

[0064] The low-reaction thermal mineral reinforcement material comprises component A and component B in a mass ratio of 1:1.05;

[0065] The A component includes the following raw materials in parts by weight:

[0066] Polyether polyol A: 75 parts;

[0067] INOVOL R3003: 15 parts;

[0068] TCPP: 10 copies;

[0069] Catalyst: 0.5 parts;

[0070] The preparation method of the polyether polyol A is as follows: 200g of bisphenol F and 85.7g of liquid sorbitol (content of 70wt.%) are put into a reactor, and 7g of tetradecene tertiary amine is added at the same time. After the reactor is closed for leak testing and replacement, the temperature is raised to 110±5°C under a nitrogen atmosphere, and vacuum bubbling is performed for dehydration for 1.5h; after dehydration, the temperature is lowered to 87.5±2.5°C, 105g of propylene oxide is added dropwise, and the pressure of the reactor is controlled below 0.35Mpa during the addition process. After the addition is completed, the temperature is raised to 120±5°C, and the remaining 348g of propylene oxide is added dropwise, and the pressure of the reactor is controlled below 0.35Mpa during the addition process. After the addition is completed, the pressure of the reactor is maintained at 0.3±0.1Mpa, and the internal pressure is 2h. After the internal pressure is completed, the temperature is lowered to 100°C for nitrogen bubbling to remove residual small molecules. After bubbling for 1 hour, the temperature was lowered and the material was discharged to obtain polyether polyol A with a hydroxyl value of 311 mgKOH / g and a viscosity of 2612 mPa·s.

[0071] The catalyst is a mixture of potassium acetate and dibutyltin dilaurate in a mass ratio of 5:1;

[0072] The B component includes the following raw materials in parts by weight:

[0073] Prepolymer: 75 parts;

[0074] TCPP: 20 copies;

[0075] Propylene carbonate: 5 parts;

[0076] The prepolymer is prepared by reacting 44V20 and INOVOL C210FR at a mass ratio of 100:37 at 70° C. for 2 hours.

[0077] The method for preparing the low-reaction thermal mineral reinforcement material comprises the following steps:

[0078] (1) Polyether polyol A, INOVOL R3003, TCPP and catalyst were placed in a stirred tank and stirred at room temperature for 1 hour to obtain component A with a viscosity of 456 mPa·s;

[0079] (2) The prepolymer, TCPP and propylene carbonate were placed in a stirred tank and stirred at room temperature for 1 hour to obtain component B with a viscosity of 467 mPa·s;

[0080] (3) Mix component A and component B in a mass ratio of 1:1.05 and pour into a mold. After curing at room temperature for 8 minutes, open the mold to obtain a low-reaction thermal reinforcement material for minerals with an expansion multiple of 1.

[0081] Example 3

[0082] The low-reaction thermal mineral reinforcement material comprises component A and component B in a mass ratio of 1:1.05;

[0083] The A component includes the following raw materials in parts by weight:

[0084] Polyether polyol A: 70 parts;

[0085] INOVOL R3003: 20 parts;

[0086] TCEP: 10 parts;

[0087] Catalyst: 0.6 parts;

[0088] The preparation method of the polyether polyol A is as follows: 250g of bisphenol S and 85.7g of liquid sorbitol (content 70wt.%) are put into a reactor, and 8g of triethylamine is added at the same time. After the reactor is closed for leak testing and replacement, the temperature is raised to 110±5°C under a nitrogen atmosphere, and vacuum bubbling is performed for dehydration for 1.5h; after dehydration, the temperature is lowered to 87.5±2.5°C, 100g of propylene oxide is added dropwise, and the pressure of the reactor is controlled below 0.35Mpa during the addition process. After the addition is completed, the temperature is raised to 120±5°C, and the remaining 303g of propylene oxide is added dropwise, and the pressure of the reactor is controlled below 0.35Mpa during the addition process. After the addition is completed, the pressure of the reactor is maintained at 0.3±0.1Mpa, and the internal pressure is 3h. After the internal pressure is completed, the temperature is lowered to 100°C for nitrogen bubbling to remove residual small molecules. After bubbling for 1 hour, the temperature was lowered and the material was discharged to obtain polyether polyol A with a hydroxyl value of 308 mgKOH / g and a viscosity of 1987 mPa·s.

[0089] The catalyst is a mixture of potassium acetate and dibutyltin dilaurate in a mass ratio of 5:1;

[0090] The B component includes the following raw materials in parts by weight:

[0091] Prepolymer: 80 parts;

[0092] TCEP: 13 copies;

[0093] Propylene carbonate: 7 parts;

[0094] The prepolymer is prepared by reacting M20S and INOVOL C210FR at a mass ratio of 100:35.5 at 60° C. for 3 hours.

[0095] The method for preparing the low-reaction thermal mineral reinforcement material comprises the following steps:

[0096] (1) Polyether polyol A, INOVOL R3003, TCEP and catalyst were placed in a stirred tank and stirred at room temperature for 2 hours to obtain component A with a viscosity of 421 mPa·s;

[0097] (2) The prepolymer, TCEP and propylene carbonate were placed in a stirred tank and stirred at room temperature for 2 hours to obtain a component B with a viscosity of 480 mPa·s;

[0098] (3) Mix component A and component B in a mass ratio of 1:1.05 and pour into a mold. After curing at room temperature for 8 minutes, open the mold to obtain a low-reaction thermal reinforcement material for minerals with an expansion multiple of 1.

[0099] Comparative Example 1

[0100] The reinforcing material comprises component A and component B in a mass ratio of 1:1.05;

[0101] The A component includes the following raw materials in parts by weight:

[0102] Polyether polyol INOVOL C305: 62 parts;

[0103] INOVOL R3003: 28 parts;

[0104] TCEP: 10 parts;

[0105] Catalyst: 0.6 parts;

[0106] The catalyst is a mixture of potassium acetate and dibutyltin dilaurate in a mass ratio of 4:1;

[0107] The B component includes the following raw materials in parts by weight:

[0108] Prepolymer: 80 parts;

[0109] TCEP: 15 parts;

[0110] Propylene carbonate: 5 parts;

[0111] The prepolymer is prepared by reacting PM200 and INOVOL C210FR at a mass ratio of 100:34 at 60° C. for 3 hours.

[0112] The method for preparing the reinforcement material comprises the following steps:

[0113] (1) Put polyether polyol INOVOL C305, INOVOL R3003, TCEP and catalyst into a stirred tank and stir at room temperature for 2 hours to obtain component A with a viscosity of 387 mPa·s;

[0114] (2) The prepolymer, TCEP and propylene carbonate were placed in a stirred tank and stirred at room temperature for 2 h to obtain component B with a viscosity of 512 mPa·s;

[0115] (3) Mix component A and component B in a mass ratio of 1:1.05 and pour into a mold. Curing at room temperature for 8 minutes and opening the mold will give the reinforced material with an expansion multiple of 1.

[0116] Comparative Example 2

[0117] The difference from Example 2 is that component B is a prepolymer synthesized from 44V20 and INOVOL C210 at 70° C. The rest is the same as Example 2.

[0118] The reinforcement materials prepared in Examples 1 to 3 and Comparative Examples 1 to 2 were subjected to performance tests, and the test methods were as follows:

[0119] Compressive strength (MPa): Tested in accordance with GB / T 2567-2008;

[0120] Reaction heat (℃): Tested in accordance with AQT-1089-2020 Polymer Materials for Coal Rock Reinforcement in Coal Mines Part 5: Maximum Reaction Temperature;

[0121] Oxygen index (%): Tested in accordance with GB / T 2406.2-2009;

[0122] The test results are shown in Table 1.

[0123] Table 1 Performance test results

[0124]

[0125] It can be seen from the data in Table 1 that the reaction heat of the low reaction heat mining reinforcement materials obtained in Examples 1-3 is all below 92°C, while the compressive strength is all above 58MPa, and the oxygen index is above 28, meeting the requirements of mining reinforcement materials for reaction heat ≤100°C, compressive strength ≥40MPa, and oxygen index ≥28.

[0126] In Comparative Example 1, since the polyether polyol INOVOL C305 used in component A does not contain a benzene ring structure, the strength of the obtained reinforcement material is relatively low.

[0127] In Comparative Example 2, since component B uses INOVOL C210 which does not contain bromine, its oxygen index is relatively low and its flame retardant performance does not meet the requirements of mining reinforcement materials.

Claims

1. A low-reaction thermal reinforcement material for mining, characterized in that: It includes component A and component B in a mass ratio of 1:1.05; The A component includes the following raw materials in parts by weight: Polyether polyol A: 70-75 parts; Polyether polyol B: 15-20 parts; Flame retardant: 10 parts; Catalyst: 0.5-0.6 parts; Wherein, the polyether polyol A uses bisphenol compounds and sorbitol as mixed initiators, has a functionality of 3, and a hydroxyl value of 305-315 mgKOH / g; The polyether polyol B uses sucrose and sorbitol as mixed initiators, has a functionality of 7, and a hydroxyl value of 140-180 mgKOH / g; The B component includes the following raw materials in parts by weight: Prepolymer: 75-80 parts; Flame retardant: 13-20 parts; Viscosity reducer: 5-7 parts; The prepolymer is prepared by addition polymerization of polymerized MDI and polyether polyol C in a mass ratio of 100:(34-37); the polyether polyol C uses tetrabromobisphenol A and diol as mixed initiators, and has a hydroxyl value of 102-122 mgKOH / g.

2. The low-reaction thermal reinforcement material for mining according to claim 1, characterized in that: The polyether polyol A is prepared by using a bisphenol compound and sorbitol in a mass ratio of (3-4.5):1 as a mixed initiator, and catalyzing the ring-opening polymerization of alkylene oxide under the action of an alkaline catalyst, and has a viscosity of 1900-2700 mPa·s.

3. The low-reaction thermal reinforcement material for mining according to claim 2, characterized in that: The bisphenol compound is one of bisphenol A, bisphenol S or bisphenol F; the alkaline catalyst is dodeca-tertiary amine or triethylamine.

4. The low-reaction thermal reinforcement material for mining according to claim 1, characterized in that: The viscosity of the polyether polyol B is 700-1500 mPa·s.

5. The low-reaction thermal reinforcement material for mining according to claim 1, characterized in that: The viscosity of the polyether polyol C is 800-2000 mPa·s.

6. The low-reaction thermal reinforcement material for mining according to claim 1, characterized in that: The flame retardant is one of TCPP, TCEP or TEP.

7. The low-reaction thermal reinforcement material for mining according to claim 1, characterized in that: The catalyst is a mixture of potassium acetate and dibutyltin dilaurate, and the mixing mass ratio is (4-5):

1.

8. The low-reaction thermal reinforcement material for mining according to claim 1, characterized in that: The preparation conditions of the prepolymer are: reacting at 60-70° C. for 2-3 hours.

9. The low-reaction thermal reinforcement material for mining according to claim 1, characterized in that: The viscosity reducing agent is propylene carbonate.

10. A method for preparing a low-reaction thermal reinforcement material for mining as claimed in any one of claims 1 to 9, characterized in that: The following steps are involved: (1) Put polyether polyol A, polyether polyol B, flame retardant and catalyst into a stirred tank and stir at room temperature for 1-2 hours to obtain component A; (2) Add the prepolymer, flame retardant and viscosity reducer into a stirring kettle and stir at room temperature for 1-2 hours to obtain component B; (3) Mix component A and component B in a mass ratio of 1:1.05 and pour into a mold. After solidification and mold opening, a low-reaction thermal ore reinforcement material is obtained.

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