阅读说明：本技术 铁路隧道混凝土用防结冰、抗侵蚀材料及其制作方法 (Anti-icing and anti-erosion material for railway tunnel concrete and manufacturing method thereof ) 是由 吴玉哲 何晓文 胡江海 倪国华 梁鹏江 陈虎林 于 2021-06-24 设计创作，主要内容包括：本发明涉及工程修复技术领域。目的在于提供铁路隧道混凝土用防结冰、抗侵蚀材料,包括组分A和组分B,所述组分A和组分B按照1-3:1的重量比配置；所述组分A按重量份包括如下原材料：改性环氧树脂66-76份、活性稀释剂11-21份和增韧剂11-21份,所述改性环氧树脂是利用聚醇对双酚环氧树脂改性获得；所述组分B按重量份包括如下原材料：改性合成酚醛胺75-85份、聚醚胺5-15份和促进剂5-15份；所述改性合成酚醛胺利用长链酚和醛与低分子多胺进行曼尼希反应改性获得。本发明能够消除环氧树脂初期反应的收缩,使得其与潮湿面的粘结强度高,降低复漏风险,综合性能优异。(The invention relates to the technical field of engineering repair. The anti-icing and anti-corrosion material for the railway tunnel concrete comprises a component A and a component B, wherein the component A and the component B are configured according to the weight ratio of 1-3: 1; the component A comprises the following raw materials in parts by weight: 66-76 parts of modified epoxy resin, 11-21 parts of reactive diluent and 11-21 parts of toughening agent, wherein the modified epoxy resin is obtained by modifying bisphenol epoxy resin by using polyalcohol; the component B comprises the following raw materials in parts by weight: 75-85 parts of modified synthetic phenolic amine, 5-15 parts of polyether amine and 5-15 parts of accelerator; the modified synthetic phenolic aldehyde amine is obtained by performing Mannich reaction modification on long-chain phenol, aldehyde and low-molecular polyamine. The invention can eliminate the shrinkage of the initial reaction of the epoxy resin, so that the bonding strength of the epoxy resin and a wet surface is high, the risk of repeated leakage is reduced, and the comprehensive performance is excellent.)

1. Anti-icing, anti-erosion material for railway tunnel concrete, its characterized in that: the paint comprises a component A and a component B, wherein the component A and the component B are configured according to the weight ratio of 1-3: 1;

the component A comprises the following raw materials in parts by weight: 66-76 parts of modified epoxy resin, 11-21 parts of reactive diluent and 11-21 parts of toughening agent, wherein the modified epoxy resin is obtained by modifying bisphenol epoxy resin by using polyalcohol;

the component B comprises the following raw materials in parts by weight: 75-85 parts of modified synthetic phenolic amine, 5-15 parts of polyether amine and 5-15 parts of accelerator; the modified synthetic phenolic aldehyde amine is obtained by performing Mannich reaction modification on long-chain phenol, aldehyde and low-molecular polyamine.

2. The ice-preventive and erosion-resistant material for railway tunnel concrete according to claim 1, wherein said component A and component B are disposed in a weight ratio of 2: 1.

3. The ice-preventing and erosion-preventing material for railway tunnel concrete according to claim 1, characterized in that: the toughening agent is flexible epoxy resin.

4. The ice-preventing and erosion-preventing material for railway tunnel concrete according to claim 2, characterized in that: the modified epoxy resin in the component A is prepared from the following raw materials in parts by weight: 95-105 parts of bisphenol F epoxy resin, 1-10 parts of polyalcohol, 0.10-0.15 part of thixotropic agent and 0.4-0.6 part of catalyst.

5. The ice-proof and erosion-resistant material for railway tunnel concrete according to claim 4, wherein: the component A comprises the following raw materials in parts by weight: 100 parts of bisphenol F epoxy resin, 2 parts of polyol, 0.1 part of thixotropic agent, 0.5 part of catalyst, 20 parts of reactive diluent and 20 parts of flexible epoxy resin.

6. The ice-proof and erosion-resistant material for railway tunnel concrete according to claim 5, wherein: the component A is prepared by the following method:

s1, weighing bisphenol F type epoxy resin, a catalyst and a thixotropic agent according to the parts by weight, adding the materials into a reaction kettle, heating the materials to 120 ℃, adding polyol, raising the temperature to 130 +/-2 ℃ after adding the polyol, continuing to react for 1-2h, and cooling the mixture to obtain modified epoxy resin;

and S2, mixing the modified epoxy resin, the reactive diluent and the toughening agent according to the parts by weight, and uniformly stirring to obtain the component A.

7. The ice-preventing and erosion-preventing material for railway tunnel concrete according to claim 6, wherein: the modified synthetic phenolic aldehyde amine in the component B is prepared from the following raw materials in parts by weight: 20-30 parts of low-molecular-weight polyamine, 45-55 parts of long-chain phenol and 4-6 parts of aldehyde.

8. The ice-preventing and erosion-preventing material for railway tunnel concrete according to claim 7, wherein: the component B comprises the following raw materials in parts by weight: 100 parts of long-chain phenol, 12 parts of aldehyde, 50 parts of low-molecular polyamine, 20 parts of polyether amine and 20 parts of accelerator.

9. The ice-preventing and erosion-preventing material for railway tunnel concrete according to claim 8, wherein: the component B is prepared by the following method:

s1, adding long-chain phenol and low-molecular polyamine into a reactor with reflux condensation, heating to 50 ℃, adding aldehyde in batches while stirring, heating the system to 80 +/-5 ℃, carrying out reflux reaction for 3 hours, and cooling to 50 ℃;

and S2, adding the polyether amine and the accelerator according to the parts by weight, and stirring and mixing uniformly to obtain the component B.

10. The ice-preventing and erosion-preventing material for railway tunnel concrete according to claim 9, wherein: the thixotropic agent is prepared from the following raw materials in parts by weight: 27.5 parts of polyether polyol, 11 parts of TDI polymer, 9 parts of HDI polymer, 51 parts of N-methylpyrrolidone, 1.6 parts of hexamethylene diamine, 49 parts of polyamide wax powder, 12.2 parts of dimethylbenzene, 31 parts of allyl polyether and 28.8 parts of hydrogen-containing silicone oil.

Technical Field

The invention relates to the technical field of engineering repair, in particular to an anti-icing and anti-erosion material for railway tunnel concrete and a manufacturing method thereof.

Background

When the tunnel passes through a water-bearing stratum and a rock fusion crack development section, water leakage of the tunnel can be formed, and when the temperature of air in the tunnel is reduced to about 0 ℃ in winter, the water leakage section is often frozen. After part of ice is formed, the water leakage hole can be sealed, and when the ice is seriously developed, the ice can invade the limit to influence the driving safety. In the electric traction section, the tunnel arch part leaks water to cause tripping and discharging leakage of a contact network, the railway safety operation is influenced, the locomotive or a pantograph is scratched by the overlong length of the ice hanger, and the locomotive is impacted by the broken and dropped ice hanger. If the insulator on the roof is subjected to flashover discharge, large short-circuit current can form electric arcs, contact wires are burnt out, railway transportation is stopped, and disasters are further expanded. In severe cold areas, the water leakage of the tunnel can cause the side wall to be frozen, the arch part to be hung with ice, the side wall enters the limit and the normal use of the tunnel is influenced. The permeable chloride ions of the tunnel aquifer seriously exceed the standard of the concrete can erode the durability of the concrete in the saturated state of the chloride ion water for a long time, the long-term service life of the concrete is influenced, and the concrete is formed to be loose and fall off, the compressive strength is reduced, alkali aggregate reaction, cracks are increased and the like. The ice layer can be continuously accumulated on the surface of the material, and great influence is brought to production and life. For example, the ice layer is continuously accumulated on the railway steel rail, so that the load of the railway vehicle is increased, the wheel abrasion is increased, the running of the railway locomotive is influenced, and great potential safety hazard is generated.

The tunnel lining and related equipment are corroded by the water leakage caused by the wind tunnel, the vibration principle and the concrete lining microcracks generated by deformation of the tunnel, the lining structure is damaged, surrounding rock deformation is caused, the bearing capacity of reinforcing steel bars and concrete is reduced, the service life of the equipment is shortened, the maintenance cost is increased, the soil behind the supporting structure can be hollowed by the water leakage for a long time, and a cavity is formed behind the supporting structure, meanwhile, the surrounding rock is loosened, so that the grade of the surrounding rock is reduced, the running time of the structural load is increased by more than 10 years, the structural state of the tunnel lining is basically stable, the tunnel lining and the lining have no settlement, displacement and concrete dislocation exceeding the limit, in the process of renovating the vault hollow of the tunnel, as the skylight time of the operation railway is very short, only 3 to 4 hours, in addition, the operation space is limited in the operation railway tunnel, and phenomena of cracking and chipping of the lining and the like exist. Through knocking inspection, the lining thickness is mostly insufficient to cause, and the cracking and the chipping of the lining become the biggest threat of railway operation safety. The existence of lining gap defects has the possibility of increasing the relaxation coefficient of surrounding rocks, increasing local lining load and increasing the ground subsidence. According to the research of Wanglihua, when the thickness of the arch part of the tunnel lining is less than 50% of the designed thickness, the deformation of the arch lining structure is larger than that of the lining structures at other positions. Due to the quality defect of the lining, the stress of the lining is uneven, the stress condition of the lining is worsened, the stress state of the lining design is changed, the actual stress of the lining possibly exceeds the design stress range, the tunnel lining has damage probability under the action of external load and other adverse factors, the frost damage can be further caused in cold regions, the lining concrete frost heaving cracking is caused, and the arch wall is deformed and damaged.

It can be seen from this, railway tunnel vault seepage problem, it is an important problem that influences railway driving safety all the time, interior infiltration water can cause the lining cutting to denudate, the country rock softens, the lining cutting is vacated behind one's back, cause railway tunnel structure load to change, be unfavorable for stable in structure, tunnel seepage's harm can also lead to the tunnel bottom to sink simultaneously, basement deformation fracture, it sends out mud to probably take place to turn over the thick liquid, influence the circuit ride comfort, serious can lead to the tunnel fracture, the wrong platform or big deformation, concrete structure durability receives serious influence, and the easy ice slush that appears in winter pounds the car, damage condition such as walking equipment, influence railway driving safety. Therefore, in the later maintenance process of the railway tunnel, the repairing material is required to be used for repairing and filling the water seepage seam of the vault, and in the repairing and filling process, the material is required to have comprehensive performance requirements of environmental protection, no toxicity, compactness, durability, no foam, wet bonding, elastic adaptability, high structural strength, strong flexibility, short condensation time and the like, and the existing material is difficult to meet the comprehensive requirements of various indexes at present and has poor application effect.

For example: 1. the 'epoxy resin' is originally a net material reinforced by a dry surface of a structure, is not suitable for water plugging, has the fatal defects of serious loss of curing performance in water and serious repeated leakage caused by incapability of adapting to crack stretching deformation, mainly refers to oily epoxy or hydrophilic curing agent oily epoxy, and is not suitable for plugging because of serious shrinkage of aqueous epoxy. 2. The acrylate is a gel, the interior of which is basically water, basically has no viscous force and strength, has serious water loss shrinkage, is easy to extrude by external force, but can be instantly solidified, has extremely low viscosity and good pourability, and can be used for temporarily blocking large water. The 'oil-based polyurethane foaming agent' expands to block and crack after reacting with water to achieve the purpose of stopping water, but the high expansion may cause secondary damage to a structure and a foam-shaped curing structure, has no elasticity, is poor in durability, cannot adapt to expansion and shrinkage deformation of cracks, and is serious in repeated leakage, but can also be used for temporary leakage stopping or emergency engineering due to fast solidification. 4. The 'aqueous urethane foaming agent' expands when meeting water to become a colloidal consolidation body, has high reaction speed relative to oiliness, can block urgent water and has strong impermeability, and the fatal defects are that the volume change is large due to high water content and severe water loss shrinkage, and the re-leakage rate is high and can be used for temporary blocking or emergency engineering like oiliness.

Disclosure of Invention

The invention aims to provide an anti-icing and anti-erosion material for railway tunnel concrete, which has excellent comprehensive performance and can effectively meet the current water leakage repair requirement of the vault of a railway tunnel.

In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows: the anti-icing and anti-corrosion material for the railway tunnel concrete comprises a component A and a component B, wherein the component A and the component B are prepared according to the weight ratio of 1-3: 1;

the component A comprises the following raw materials in parts by weight: 66-76 parts of modified epoxy resin, 11-21 parts of reactive diluent and 11-21 parts of toughening agent, wherein the modified epoxy resin is obtained by modifying bisphenol epoxy resin by using polyalcohol;

the component B comprises the following raw materials in parts by weight: 75-85 parts of modified synthetic phenolic amine, 5-15 parts of polyether amine and 5-15 parts of accelerator; the modified synthetic phenolic aldehyde amine is obtained by performing Mannich reaction modification on long-chain phenol, aldehyde and low-molecular polyamine.

Preferably, the toughening agent is a flexible epoxy resin.

Preferably, the modified epoxy resin in the component A is prepared from the following raw materials in parts by weight: 95-105 parts of bisphenol F epoxy resin, 1-10 parts of polyalcohol, 0.10-0.15 part of thixotropic agent and 0.4-0.6 part of catalyst.

Preferably, the component A comprises the following raw materials in parts by weight: 100 parts of bisphenol F epoxy resin, 2 parts of polyol, 0.1 part of thixotropic agent, 0.5 part of catalyst, 20 parts of reactive diluent and 20 parts of flexible epoxy resin.

Preferably, the component A is prepared by the following method:

s1, weighing bisphenol F type epoxy resin, a catalyst and a thixotropic agent according to the parts by weight, adding the materials into a reaction kettle, heating the materials to 120 ℃, adding polyol, raising the temperature to 130 +/-2 ℃ after adding the polyol, continuing to react for 1-2h, and cooling the mixture to obtain modified epoxy resin;

and S2, mixing the modified epoxy resin, the reactive diluent and the toughening agent according to the parts by weight, and uniformly stirring to obtain the component A.

Preferably, the modified synthetic phenolic aldehyde amine in the component B is prepared from the following raw materials in parts by weight: 20-30 parts of low-molecular-weight polyamine, 45-55 parts of long-chain phenol and 4-6 parts of aldehyde.

Preferably, the component B comprises the following raw materials in parts by weight: 100 parts of long-chain phenol, 12 parts of aldehyde, 50 parts of low-molecular polyamine, 20 parts of polyether amine and 20 parts of accelerator.

Preferably, the component B is prepared by the following method:

s1, adding long-chain phenol and low-molecular polyamine into a reactor with reflux condensation, heating to 50 ℃, adding aldehyde in batches while stirring, heating the system to 80 +/-5 ℃, carrying out reflux reaction for 3 hours, and cooling to 50 ℃;

and S2, adding the polyether amine and the accelerator according to the parts by weight, and stirring and mixing uniformly to obtain the component B.

Preferably, the thixotropic agent is prepared from the following raw materials in parts by weight: 27.5 parts of polyether polyol, 11 parts of TDI polymer, 9 parts of HDI polymer, 51 parts of N-methylpyrrolidone, 1.6 parts of hexamethylene diamine, 49 parts of polyamide wax powder, 12.2 parts of dimethylbenzene, 31 parts of allyl polyether and 28.8 parts of hydrogen-containing silicone oil.

Preferably, the thixotropic agent is prepared by the following method, adding polyamide wax powder, xylene and allyl polyether into a reaction kettle, heating to 80-83 ℃, then adding polyether polyol, TDI polymer and HDI polymer into the reaction kettle, reacting for 4-5h at the temperature of 60-80 ℃, adding N-methylpyrrolidone and hexamethylenediamine when the NCO value of isocyanate group in the reaction kettle reaches 19-20, reacting for 1.2-3.2h, vacuumizing, physically removing water, performing nitrogen protection, and then adding hydrogen-containing silicone oil for reacting for 3.2-8.2h to obtain the thixotropic agent.

The beneficial effects of the invention are concentrated and expressed as follows:

1. the invention changes the condition that the epoxy resin has a certain volume shrinkage rate during curing, and the polyethylene chain is inserted into the main chain through the reaction with the polyalcohol and slowly expands when meeting water, so that the shrinkage of the initial reaction of the epoxy resin can be eliminated during construction plugging, and the bonding strength between the epoxy resin and a wet surface is high.

2. The main chain of the flexible epoxy resin is free from rigid benzene rings, the molecular chain can rotate freely and is flexible, and the added moderate flexible epoxy resin serving as a toughening agent can improve the overall toughness of the plugging material, improve the elasticity of the plugging material, ensure the structural strength of plugging, have elastic self-adaptive capacity when the structure of a structural joint and a water seepage joint changes, and reduce the risk of repeated leakage.

3. In the mannich reaction, aliphatic aldehydes and amines are selected to react, so that the flexibility of the curing agent is increased. However, the activity of the curing agent is reduced due to the long chain, so that low-molecular polyamine, polyether amine and aldehyde are selected as reaction raw materials, wherein the low-molecular polyamine has high activity, plays a role in rapid curing and meets the requirement of railway construction skylight points. The polyether amine has high flexibility and plays a toughening role. The phenol is used as a framework, and long-chain phenol is selected, so that the flexibility is good. Meanwhile, the flexible material can repair the structural defects of the concrete at the interface, so that the elastic modulus structure of the interface is more perfect.

4. The invention has low initial viscosity, ensures the operability of grouting in the construction process, improves the permeability of slurry, improves the tightness of plugging, improves the meshing tightness between new and old concrete through the effective permeation of materials, inhibits the cracking of a bonding surface and ensures the plugging strength.

Drawings

FIG. 1 is a block diagram of the preparation process of component A according to the present invention;

FIG. 2 is a block diagram of the preparation process of component B of the present invention;

FIG. 3 is a graph of the effect of reactive diluent content on component A viscosity;

FIG. 4 is a graph of the effect of reactive diluent content on the compressive strength of a consolidated body;

FIG. 5 is a graph of the effect of toughener content on component A viscosity;

FIG. 6 is a graph of the effect of toughening agent content on the compressive strength of a consolidated body;

FIG. 7 is a graph of the effect of toughener content on consolidated body elongation;

FIG. 8 is a Mannich reaction infrared spectrum;

FIG. 9 shows a sample of the present invention microscopically bonded to a mortar bond interface;

FIG. 10 shows the three-dimensional network structure formed by the mortar during the combination process of the sample and the mortar under the microscope.

Detailed Description

The novel material is a bi-component material and comprises a component A and a component B, wherein the component A is formed by stirring and mixing modified epoxy resin generated by reacting bisphenol epoxy resin with polyalcohol, a toughening agent and an active diluent, a main chain of the flexible epoxy resin does not have a rigid benzene ring, a molecular chain can freely rotate and is flexible, and the addition of proper flexible epoxy resin can improve the overall elasticity of the material after solidification, but the epoxy value cannot be too small, otherwise the activity of the material is influenced. The component B is essentially a curing agent and is prepared by mixing modified low-molecular-weight polyamine, polyether amine and an accelerant after the modified low-molecular-weight polyamine is subjected to Mannich reaction modification of long-chain phenol and aldehyde. The components A and B are uniformly mixed according to a certain proportion, poured into a leakage position, and quickly cured into a solidification body with certain flexibility to play a role in quickly blocking water and reinforcing, and the preparation proportion of the components A and B can be adjusted according to actual needs in principle, but the proportion of the components A and B is usually 1-3:1, wherein experiments prove that 2:1 is preferred.

When the components A and B are prepared, the respective reaction principles are as follows:

(1) component A

Firstly, hydroxyl contained in the dihydroxy compound polyalcohol reacts with a small part of epoxy groups of the epoxy resin, and after the small part of epoxy groups react with the dihydroxy compound, a flexible chain segment is introduced into a main chain of the epoxy resin, so that the flexibility of the chain is increased, the bisphenol epoxy resin has the performance of fatty alcohol, and the viscosity of the epoxy resin can be effectively reduced; the reaction principle is as follows:

adding the modified epoxy resin into an epoxy diluent for diluting, adding a toughening agent for toughening, wherein the toughening agent is usually flexible epoxy resin, and uniformly mixing to obtain a component A;

of course, to further enhance the final plugging consolidation properties, a thixotropic agent may also be added, said thixotropic agent of the present invention being described in detail below.

As shown in fig. 1, component a is specifically prepared in the following manner:

s1, weighing bisphenol F type epoxy resin, a catalyst and a thixotropic agent according to the parts by weight, adding the materials into a reaction kettle, heating the materials to 120 ℃, adding polyol, raising the temperature to 130 +/-2 ℃ after adding the polyol, continuing to react for 1-2h, and cooling the mixture to obtain modified epoxy resin;

and S2, mixing the modified epoxy resin, the reactive diluent and the toughening agent according to the parts by weight, and uniformly stirring to obtain the component A.

(2) B component

Firstly, modifying low-molecular polyamine through a Mannich reaction to obtain modified synthetic phenolic aldehyde amine, wherein in the Mannich reaction, aliphatic aldehyde and amine are preferably selected for reaction, and aromatic aldehyde and aromatic amine are not preferably adopted, so that the flexibility of the curing agent is increased. But the long chain is favorable for reducing the activity of the curing agent, so that low-molecular polyamine, long-chain phenol and aldehyde are selected as reaction raw materials, and the modified synthetic phenolic aldehyde amine is mixed with the polyether amine and the accelerator. Wherein, the low molecular polyamine has high activity and rapid curing effect, and the polyether amine has high flexibility and toughening effect. The phenol is used as a framework, long-chain phenol is selected, the flexibility is good, and the reaction principle is as follows:

and (3) uniformly mixing the modified low-molecular-weight polyamine, the polyether amine and the accelerator to obtain a component B.

As shown in fig. 2, component B was specifically prepared in the following manner:

s1, adding long-chain phenol and low-molecular polyamine into a reactor with reflux condensation, heating to 50 ℃, adding aldehyde in batches while stirring, heating the system to 80 +/-5 ℃, carrying out reflux reaction for 3 hours, and cooling to 50 ℃;

and S2, adding the polyether amine and the accelerator according to the parts by weight, and stirring and mixing uniformly to obtain the component B.

With respect to thixotropic agents

The thixotropic agent is prepared from the following raw materials in parts by weight: 27.5 parts of polyether polyol, 11 parts of TDI polymer, 9 parts of HDI polymer, 51 parts of N-methylpyrrolidone, 1.6 parts of hexamethylene diamine, 49 parts of polyamide wax powder, 12.2 parts of dimethylbenzene, 31 parts of allyl polyether and 28.8 parts of hydrogen-containing silicone oil. The thixotropic agent is prepared by the following method, polyamide wax powder, dimethylbenzene and allyl polyether are added into a reaction kettle, the mixture is heated to 80-83 ℃, polyether polyol, TDI polymer and HDI polymer are then injected into the reaction kettle, the reaction is carried out for 4-5 hours at the temperature of 60-80 ℃, N-methyl pyrrolidone and hexamethylene diamine are added when the NCO value of isocyanate group in the reaction kettle reaches 19-20, the reaction is carried out for 1.2-3.2 hours, vacuum pumping is carried out after physical moisture removal, nitrogen protection is carried out, and then hydrogen-containing silicone oil is added for reaction for 3.2-8.2 hours, so that the thixotropic agent is obtained.

Verification experiment

The invention will be described with reference to the experimental results.

In the verification process, the test method is as follows:

(ii) density of the slurry

The density of the slurry component A, B after mixing was determined according to GB/T13354-.

Initial viscosity of slurry

The initial viscosity of the slurry components A, B after mixing was determined as in GB/T2794-1995.

③ initial gel time in water

Under standard laboratory conditions (temperature (23 + -2) ° c, relative humidity (50 + -10)%), slurry components A, B were mixed uniformly in a certain mass ratio and 45 g were weighed, and poured into a 250ml glass beaker to spread uniformly. A 250ml glass beaker was placed in a 3000ml glass beaker and water was poured into the 3000ml mark. The surface of the slurry mix was contacted with a glass rod every 10min until "stringing" occurred. The time elapsed at this time was recorded and this time was the initial gel time of the epoxy lost circulation material in water. The accuracy is 10 min.

Elongation at break

The concretes were tested for elongation at break according to GB/T2568-1995.

Compressive strength-

The compressive strength of the consolidated body is measured according to GB/T2569-1995 for tensile strength, and the calculation result is accurate to 1 MPa. The sample size was 10mm diameter and 25mm high cylinder.

Underwater adhesive strength

Preparation of a test piece: preparing the 8-shaped mortar block according to the requirements of GB/T16777-. Adopting ordinary Portland cement with the strength grade of 42.5, adding cement and medium sand into a mortar stirrer according to the mass ratio of 1:1, stirring, pouring water with the mortar consistency (70-90) mm as the standard, vibrating and leveling the mixture in a mold frame, moving the mixture into a curing room, demolding after 1d, curing the mixture in water for 10d, drying the mixture in an oven at the temperature of (50 +/-2) DEG C for 24 +/-0.5 h, taking out the dried mixture, placing the dried mixture for later use under the standard addition, and preparing 5 pairs of mortar test blocks in the same way.

Test apparatus: tensile testing machine, tensile speed (5 +/-1) mm/min.

The test steps are as follows: the 8-shaped die is broken and soaked in water, and taken out after 24 hours. The slurry component A, B is uniformly mixed according to a certain mass ratio, coated on the cross section of an 8-shaped die, fixed by a rubber band after butt joint and adhesion, the adhesion surface is horizontally placed, immediately and completely immersed in water at 23 +/-2 ℃ for curing for 28 days, and the adhesion strength is measured after the adhesion surface is taken out.

Seventh, impermeability

The procedure was as described in JC/T1041-2007 at 7.10.

Preliminary verification

Two modified epoxy resins with added thixotropic agent are shown in table 1 below.

TABLE 1 Synthesis reaction ratio (in parts by weight) of modified epoxy resins

	Bisphenol F type epoxy resin	Polyol(s)	Thixotropic agent	Catalyst and process for preparing same
					Modified epoxy resin type 1	100	4	0.12	0.5
Modified epoxy resin type 2	100	10	0.12	0.5

The preliminary explored formulation of component a and its viscosity are shown in table 2 below.

TABLE 2 (by weight)

The preliminary explored formulation of component B is shown in table 3 below.

TABLE 3 (by weight)

The performance test of the component A, B after being mixed according to a certain proportion is as shown in the following table 4.

TABLE 4

Proportioning	Initial setting time	Compressive strength (MPa))	Elongation (%)
				A1:B1＝8：1	Implosion for 15min
A1:B1＝10：1	Implosion for 20min
				A1:B1＝100：8	Initial setting for 31min	61.9	20.3
A1:B2＝100：15	Implosion for 14min
				A1:B2＝100：12	Implosion for 16min
A1:B3＝10：1	Initial setting for 21min	74.9	21.9
				A1:B4＝100：13	Initial setting for 24min	47.9	26.8
A1:B5＝4：1	Initial setting for 30h
				A1:B5＝1：1	Initial setting for 35min	Soft cotton body	Easy to break

Watch 5 (connect table 4)

TABLE 6

By exploring the above formulas, a relatively suitable formula can be preliminarily judged, and various performances are tested:

TABLE 7 preferred formulation of component A (in parts by weight, error within + -5 parts)

Modified epoxy resin	Reactive diluent	Flexible epoxy resin
			71	16	16

TABLE 8 preferred formulation for component B (in parts by weight, error within + -5 parts)

Low molecular weight polyamines	Long chain phenols	Aldehydes	Polyether amine	Accelerator
					25	50	5	10	10

After the above preferred component A, B is mixed in a mass ratio of 2:1, its properties are as follows:

initial viscosity, mPa.s 462

② initial gel time in water, min 121

(iii) compressive Strength, MPa 46

Underwater adhesive strength, MPa 1.6

Fifthly, the anti-seepage pressure is 1.2 MPa

Sixthly, elongation at break,% 21

Optimized validation of component A

Table 9 shows the influence of the content of the reactive diluent on the properties of the component A, wherein the viscosity is the viscosity of the component A to be measured, and the compressive strength is the compressive strength of a consolidated body formed by mixing the component A to be measured with the component B in a ratio of 2:1 in Table 8, and the line graphs are respectively shown in FIG. 3 and FIG. 4.

TABLE 9

Serial number	1	2	3	4	5	6	7
								Modified epoxy resin/part	100	100	100	100	100	100	100
Reactive diluent/portion	10	15	20	25	30	35	40
								Viscosity at 20 deg.C/(mPa.s)	2010	1210	639	450	279	199	136
Compressive strength/(MPa)	80.1	71.9	60.8	52.1	43.2	35.5	25.2

As can be seen from the combination of FIGS. 3 and 4, when the viscosity is less than 1000mPa.s and the compressive strength is more than 45MPa, the performance of adding 20 parts of reactive diluent into 100 parts of modified epoxy resin is better.

On the basis, after the toughening agent is added, the influence rule of the content of the toughening agent on the performance of the serous fluid is shown in a table 10, and corresponding curve graphs are shown in fig. 5 to 7. As can be seen from Table 10, the combination of the addition of 20 parts of reactive diluent and 20 parts of toughening agent to 100 parts of modified epoxy resin is superior.

TABLE 10 impact of toughening agent content on grout Performance

Serial number	1	2	3	4	5	6	7
								Modified epoxy resin/part	100	100	100	100	100	100	100
Reactive diluent/portion	20	20	20	20	20	20	20
								Flexible epoxy resin/part	10	15	20	25	30	35	40
Viscosity at 20 deg.C/(mPa.s)	553	515	481	452	426	415	398
								Compressive strength/(MPa)	55.2	53.6	50.6	46.9	46.1	43.1	41.2
Elongation/(%)	4.1	8.2	14.6	27.5	41.2	47.3	51.2

As can be seen from the combination of FIGS. 5-7, the combination property of 100 parts of modified epoxy resin added with 20 parts of reactive diluent and 20 parts of toughening agent is better, on the basis of the formula, the bisphenol epoxy resin is modified by polyol, and then compounded according to the formula, the influence of the content of the polyol used for modification on the property of the slurry is shown in Table 11, and the combination property of the material is better when the polyol is used in 2 parts under the condition of meeting the property index of the material.

TABLE 11 Effect of polyol content used for modification on slurry Properties

Bisphenol F type epoxy resin/part	100	100	100	100	100
						Polyol/part	2	4	6	8	10
Catalyst per part	0.5	0.5	0.5	0.5	0.5
						Reactive diluent/portion	20	20	20	20	20
Flexible epoxy resin/part	20	20	20	20	20
						Viscosity at 20 deg.C/(mPa.s)	445	410	385	360	340
Compressive strength/(Mpa)	49	48	46	43	42
						Elongation/(%)	17	20	25	28	30
Underwater bonding strength/(MPa)	1.7	1.6	1.4	1.2	1.1

As can be seen from Table 11, the more preferred formulation for component A is as follows:

TABLE 12 more preferred formulation of component A

Bisphenol F type epoxy resin/part	Polyol/part	Catalyst per part	Reactive diluent/portion	Flexible epoxy resin/part
					100	2	0.5	20	20

Optimized validation of component B

TABLE 13 Effect of Low molecular weight polyamines on Material Properties

Serial number	1	2	3	4
					Long chain phenol/part	100	100	100	100
Aldehyde/part	10	10	10	10
					Low molecular weight polyamine per part	40	50	60	70
Initial setting time/min under water	190	150	130	120
					Compressive strength/(MPa)	45	55	62	70
Elongation/(%)	20	10	7	4
					Underwater bonding strength/(MPa)	1.6	1.7	1.5	1.1

TABLE 14 Effect of aldehyde usage on Material Properties

Serial number	1	2	3	4	5	6
							Long chain phenol/part	100	100	100	100	100	100
Aldehyde/part	10	12	14	10	12	14
							Low molecular weight polyamine per part	50	50	50	60	60	60
Initial setting time/min under water	150	130	120	130	120	120
							Compressive strength/(MPa)	55	60	68	62	70	75
Elongation/(%)	10	8	6	8	7	5
							Underwater bonding strength/(MPa)	1.7	1.8	1.8	1.5	1.7	1.6

Combining tables 13 and 14, it can be seen that, considering the properties of the material, the curing agent synthesized by reacting 100 parts of long-chain phenol with 12 parts of aldehyde and 50 parts of low-molecular polyamine is preferable, and on the basis of the formula, polyether amine and accelerator are added, and the test results are shown in table 15 below.

TABLE 15 influence of the amounts of polyetheramine and accelerator on the Properties of the materials

The above results show that the preferred formulation of component B is as follows:

TABLE 16 more preferred formulation of component B

As shown in the Mannich reaction infrared spectrum of FIG. 8, in the long-chain phenol infrared spectrum, the peak near 3342cm-1 is the absorption peak of phenol-OH, the peak near 1600-1400cm-1 is the absorption peak of benzene ring, the peak near 3000-2800cm-1 is the absorption peak of C-H in alkane, and the peak near 3072 cm-1 is the absorption peak of ═ C-H, which is very weak, indicating that there is a small amount of C ═ C on the long hydrocarbon chain connecting benzene ring in the long-chain phenol. In the infrared spectrum of the low molecular polyamine, the double peak of 3400-3200cm-1 region and the peak of 900-770cm-1 region are absorption peaks specific to primary amine. In the synthesized modified synthesized phenolic aldehyde amine spectrogram, the double peaks in the 3400-3200cm-1 region gradually become single peaks, the gradual disappearance of the peaks in the 900-770cm-1 region indicates that the terminal amino groups of the low-molecular polyamine are reacted, and in addition, any absorption peak of C ═ O does not appear in the 1850-1650cm-1 region, which indicates that the aldehyde is completely reacted, and the Mannich reaction is fully performed to synthesize the phenolic aldehyde amine.

In conclusion, the experimental results of the invention verify that the optimal formulas of the component A and the component B are respectively as follows:

TABLE 17 optimum formulation for component A

TABLE 18 optimum formulation for component B

TABLE 19 Performance of component A, B after mixing according to optimal formulation

Item	Target value	Measured value
			Initial viscosity, mPa.s	≤1000	420
Initial gel time in Water, min	<180	120
			Compressive strength, MPa	>40	50
Underwater adhesion strength, MPa	>1.5	1.7
			Osmotic pressure resistance, MPa	>1.0	1.2
Elongation at break,%	>5	15

The invention relates to a railway tunnel concrete anti-icing and anti-chloride ion erosion material which comprises the following components in parts by weight: the component A (namely the slurry main body) is formed by adopting the mixing proportion of modified epoxy resin, flexible epoxy resin and reactive diluent, and can meet the requirements of elasticity, high reaction activity and low viscosity. The preparation of the component B (namely the curing agent) can give consideration to flexibility and rapid curing, and the formed solidification body has good water plugging effect. Meanwhile, in the material condensation time period, the disturbance of impurity interference, cold and hot alternation and hole site plugging is solved, and the bonding property of a new interface and an old interface is improved.

As shown in fig. 9-10, are pictures of the structure of the material of the present invention at the microscopic level.