阅读说明：本技术 一种涂抹在水位变幅带内红砂岩表面改性聚氨酯材料及其制备方法 (Red sandstone surface modified polyurethane material coated in water level amplitude-variable zone and preparation method thereof ) 是由 张振华 刘泽峰 于 2020-06-08 设计创作，主要内容包括：本发明涉及一种涂抹在水位变幅带内红砂岩表面改性聚氨酯材料及其制备方法。材料包括：A组分和B组分,其中A组分包括硅酸钠溶液、催化剂、增塑剂、纳米二氧化钛；B组分包括二异氰酸酯(MDI)、聚丙二醇(PPG)、防水剂。本发明材料既拥有传统聚氨酯加固材料加固性能良好、无毒等优点,加入防水剂能有效提高该材料的耐水性能,并紧紧附着在红砂岩表面隔水与,从而隔绝水环境,以抑制红砂岩物理力学性能的劣化；最后,考虑到水位变幅带内枯水期红砂岩长期经历大量太阳紫外线辐射,造成红砂岩失水并进一部导致红砂岩表面脱落与内部开裂,最终导致红砂岩物理力学性能的劣化,加入纳米二氧化钛可以有效提高其抗老化能力。(The invention relates to a red sandstone surface modified polyurethane material coated in a water level amplitude-variable zone and a preparation method thereof. The material comprises: the component A comprises a sodium silicate solution, a catalyst, a plasticizer and nano titanium dioxide; the component B comprises diisocyanate (MDI), polypropylene glycol (PPG) and a waterproof agent. The material disclosed by the invention has the advantages of good reinforcing performance, no toxicity and the like of the traditional polyurethane reinforcing material, and the waterproof agent is added, so that the waterproof performance of the material can be effectively improved, and the material is tightly attached to the surface of the red sandstone to isolate water, so that the water environment is isolated, and the deterioration of the physical and mechanical properties of the red sandstone is inhibited; and finally, considering that the red sandstone in a low water period in the water level amplitude variation zone is subjected to a large amount of solar ultraviolet radiation for a long time, the red sandstone is dehydrated and further subjected to surface falling and internal cracking of the red sandstone, and finally the physical and mechanical properties of the red sandstone are degraded, and the ageing resistance of the red sandstone can be effectively improved by adding the nano titanium dioxide.)

1. The red sandstone surface modified polyurethane material coated in the water level amplitude-variable zone is characterized in that: the material comprises A, B components and A, B components in a volume ratio (0.5-1.5): (0.5-1.5);

the component A comprises the following components in parts by weight:

sodium silicate solution: 40-60 parts;

catalyst: 5-10 parts;

plasticizer: 5-10 parts;

nano titanium dioxide: 5-30 parts of a solvent;

the component B comprises the following components in parts by weight:

diisocyanate: 40-100 parts;

polypropylene glycol: 30-90 parts of a solvent;

water-proofing agent: 15-30 parts.

2. The red sandstone surface-modified polyurethane material smeared in a water level amplitude band according to claim 1, which is characterized in that: the sodium silicate solution: the Baume degree is 35-50 degrees, and the modulus is 2.0-3.0.

3. The modified polyurethane material smeared on the surface of the red sandstone in the water level amplitude band for water insulation and reinforcement according to claim 1, which is characterized in that: the catalyst is triethylamine or dibutyltin dilaurate or a combination thereof.

4. The modified polyurethane material smeared on the surface of the red sandstone in the water level amplitude band for water insulation and reinforcement according to claim 1, which is characterized in that: the plasticizer is dibutyl phthalate or dioctyl phthalate or triphenyl phosphate or a combination thereof.

5. The modified polyurethane material smeared on the surface of the red sandstone in the water level amplitude band for water insulation and reinforcement according to claim 1, which is characterized in that: the volume percentage content of the diisocyanate is 25-29%.

6. The modified polyurethane material smeared on the surface of the red sandstone in the water level amplitude band for water insulation and reinforcement according to claim 1, which is characterized in that: the volume percentage content of the hydroxyl specification of the polypropylene glycol is 60-62.5 mgKOH/g.

7. The modified polyurethane material smeared on the surface of the red sandstone in the water level amplitude band for water insulation and reinforcement according to claim 1, which is characterized in that: the component A also comprises the following components in parts by weight: 5-30 parts of nano titanium dioxide.

8. The modified polyurethane material smeared on the surface of the red sandstone in the water level amplitude band for water insulation and reinforcement according to claim 1, which is characterized in that: the component B also comprises the following components in parts by weight: 30-40 parts of a waterproof agent, wherein the waterproof agent is formed by mixing polyvinyl chloride, chloroprene rubber emulsion and plant fibers according to a volume ratio of 1-2: 2-4: 1-1.5.

9. The preparation method of the red sandstone surface modified polyurethane material smeared in the water level amplitude band of any one of claims 1 to 8 is characterized by comprising the following steps:

preparing a component A: adding a sodium silicate solution, adding a catalyst, a plasticizer and nano titanium dioxide in the stirring process, and stirring to obtain a component A of the reinforcement material;

preparing a component B: firstly, putting diisocyanate, polypropylene glycol and a waterproof agent into a mixing kettle, stirring uniformly, and standing to obtain a component B of the reinforcing material;

the preparation of the red sandstone surface modified polyurethane material smeared in the water level amplitude variation zone is completed.

10. Use of the material according to any one of claims 1 to 8 or the material prepared by the method according to claim 9, characterized in that: when in use, the prepared component A and the component B are mixed according to the ratio of (0.5-1.5): (0.5-1.5) by volume ratio, uniformly mixing and stirring, and coating on the surface of the red sandstone.

Technical Field

The invention belongs to the technical field of materials, and relates to a red sandstone modified polyurethane material coated in a water level amplitude-varying band and a preparation method thereof.

Background

In the reservoir water level amplitude variation zone, the rock mass is in the environment of reservoir water immersion and strong ultraviolet radiation for a long time. The rock mass is most likely to be degraded in macroscopic mechanical strength after encountering water. The main reasons for the deterioration of the strength of the red sandstone in the water level amplitude-variable zone are as follows: one is a water storage stage, reservoir water enters the rock body along the pores on the surface of the rock body under the action of osmotic pressure to perform a physical and chemical reaction with minerals, particularly a hydration reaction occurs between clay minerals in sandstone and water, so that the clay minerals absorb water and expand; in the second stage of dry water, the strong radiation and heat of sunlight cause the water in the rock to evaporate, and the clay mineral is dehydrated and contracted. The periodic operation of the reservoir can cause the periodic expansion and contraction effect of the red sandstone, so that the cementing effect among the particles in the sandstone is weakened, which is the main reason for the degradation of the macroscopic mechanical strength of the red sandstone, and the special research on the water resistance and the ageing resistance of the surface of the red sandstone in the special environment of the 'wet-dry alternation' effect of the red sandstone is few at present.

In addition, considering the special environment of the water level amplitude variation red sandstone, the reinforcing material must be non-toxic, most of the traditional polyurethane materials are used for meeting the standard requirement of flame retardance by adding flame retardants, for example, the corresponding flame retardants or additive flame retardants are generally used in the market at present, the two types of flame retardants are mainly compounds containing flame retardant elements such as phosphorus or elements, for example, 201610853385.5 a new polyurethane material uses chlorinated paraffin wax halogen-containing flame retardants. And the compound containing flame retardant elements such as phosphorus or element is easy to pollute the water quality and soil environment around the hydro-fluctuation belt. In addition, the modified polyurethane material in 201410083359.0 contains highly toxic ketones in raw materials, is easy to pollute the water quality around the reservoir, and is not suitable for reinforcing the amplitude-variable red sandstone of the reservoir.

Disclosure of Invention

In order to solve the technical problems, the invention provides the red sandstone surface modified polyurethane material coated in the water level amplitude band and the preparation method thereof, the red sandstone surface modified polyurethane material has good flame retardant property, no toxicity, strong cohesive force and water resistance, and can effectively enhance the tensile strength and compressive strength of the red sandstone and isolate the water environment.

The technical scheme adopted by the invention is as follows:

a red sandstone surface modified polyurethane material smeared in a water level amplitude-variable zone comprises the components of A,

Volume ratio of the B component, A, B component (0.5-1.5): (0.5-1.5);

the component A comprises the following components in parts by weight:

sodium silicate solution: 40-60 parts;

catalyst: 5-10 parts;

plasticizer: 5-10 parts;

nano titanium dioxide: 5-30 parts of a solvent;

the component B comprises the following components in parts by weight

Diisocyanate (MDI): 40-100 parts;

polypropylene Glycol (PPG): 30-90 parts of a solvent;

water-proofing agent: 15-30 parts.

Preferably, the sodium silicate solution: the Baume degree is 35-50 degrees, and the modulus is 2.0-3.0.

Preferably, the catalyst is triethylamine or dibutyltin dilaurate, or a combination thereof.

Preferably, the plasticizer is dibutyl or dioctyl phthalate or triphenyl phosphate or a combination thereof.

Preferably, the diisocyanate (MDI) has a (isocyanate) group content of 25-29% by volume.

Preferably, the polypropylene glycol (PPG) has a hydroxyl group specification volume percent content of 60-62.5 mgKOH/g.

Preferably, the component A also comprises the following components in parts by weight: 5-30 parts of nano titanium dioxide.

Preferably, the component B also comprises the following components in parts by weight: 30-40 parts of a waterproof agent, wherein the waterproof agent is prepared from polyvinyl chloride, chloroprene rubber emulsion and plant fibers according to a volume ratio of 1-2: 2-4: 1-1.5.

The preparation method of the red sandstone surface modified polyurethane material smeared in the water level amplitude variation zone comprises the following steps:

(1) preparing a component A: adding a sodium silicate solution, adding a catalyst, a plasticizer and nano titanium dioxide in the stirring process, and stirring to obtain a component A of the reinforcement material;

(2) preparing a component B: firstly, putting diisocyanate (MDI), polypropylene glycol (PPG) and a waterproof agent into a mixing kettle, stirring uniformly, and standing to obtain a component B of the reinforcement material;

the preparation of the red sandstone surface modified polyurethane material smeared in the water level amplitude variation zone is completed.

Preferably, the stirring temperature of the steps (1) and (2) is 15-30 ℃ and the time is 25-35 min; and (3) standing for 25-35min in the step (2).

When the material or the material prepared by the method is used, the prepared component A and the component B are mixed according to the ratio of (0.5-1.5): (0.5-1.5) by volume ratio, uniformly mixing and stirring, and coating on the surface of the red sandstone.

The invention has the beneficial effects that:

1. the material disclosed by the invention not only has the advantages of good reinforcing performance, no toxicity and the like of the traditional polyurethane reinforcing material, but also considers that the polyurethane material contains flammable hydrocarbon chain segments, and is specified in building material incombustibility test methods (GB/T5464-2010): the polyurethane material is used in important places or equipment and has to meet the corresponding requirement of flame retardance, common flame retardants containing phosphorus or elements and the like easily pollute the environment, and the addition of a sodium silicate solution can ensure that the polyurethane material can achieve good flame retardance and does not pollute the environment; considering that the red sandstone in the water storage period in the water level amplitude-changing zone is soaked by water for a long time, and the contact part of water and the red sandstone is subjected to hydration reaction to cause the deterioration of the physical and mechanical properties of the red sandstone, the waterproof agent is added to effectively improve the water resistance of the material and is tightly attached to the surface of the red sandstone to prevent water, so that the water environment is isolated, and the deterioration of the physical and mechanical properties of the red sandstone is inhibited; and finally, considering that the red sandstone in a low water period in the water level amplitude variation zone is subjected to a large amount of solar ultraviolet radiation for a long time, the red sandstone is dehydrated and further subjected to surface falling and internal cracking of the red sandstone, and finally the physical and mechanical properties of the red sandstone are degraded, and the ageing resistance of the red sandstone can be effectively improved by adding the nano titanium dioxide.

2. The component A of the invention is sodium silicate solution and CO₂Reaction takes place to produce SiO₂Inorganic tree network structure and soluble sodium carbonate crystal; a large number of sodium carbonate crystals and siloxane molecules are mutually bonded and embedded in tiny pores of the two network systems; meanwhile, a small amount of nano titanium dioxide is attached to the system, and can shield a large amount of radiation and heat of ultraviolet strong light, so that the material has good ageing resistance. Isocyanate group in diisocyanate (MDI) in the component B reacts with water in sodium silicate solution to generate carbamate high molecular compound and CO₂And the sodium silicate is used for replacing the traditional flame retardant, so that the reaction is more stable and the thermal decomposition is lower than that of the traditional polyurethane. Meanwhile, polyvinyl chloride and chloroprene rubber emulsion in the waterproof agent form a high-gel polymer crystal and a waterproof film, so that the material has strong waterproof performance.

3. Polypropylene glycol reacts with isocyanic acid radical group to generate micro-foaming polyurea macromolecule filling system inside and surface. Because the reactions are carried out simultaneously, three-dimensional inorganic structural bodies with high strength are formed, and the inorganic structural bodies and polyurea macromolecules form a high-strength network structure, so that the mechanical strength of the red sandstone is enhanced; meanwhile, polyurea macromolecules are filled in the whole network structure and are tightly attached to the surface or the gaps of the network, so that the surface of the red sandstone has good corrosion resistance.

4. The invention takes diisocyanate (MDI) as a main body, adds an inorganic modifier sodium silicate solution of polyurethane, a waterproof agent and a nano titanium dioxide material, and adds polypropylene glycol (PPG), a catalyst and a plasticizer. The reinforced material has the advantages of good reinforcing performance, no toxicity and the like of the traditional polyurethane reinforced material, has the characteristics of good flame retardant property, strong cohesive force and water resistance, and can effectively isolate an external water environment, strengthen the anti-aging capability of the reinforced material and improve the tensile strength and the compressive strength of the red sandstone.

Drawings

FIG. 1 modified polyurethane A, B component materials;

FIG. 2 shows a red sandstone sample after smearing modified polyurethane;

FIG. 3 shows a water absorption test sample of the modified polyurethane;

FIG. 4 is a test result curve of water absorption rate of the modified polyurethane under different high-temperature bath water conditions.

Detailed Description