Novel environment-friendly epoxy resin grouting material and production method thereof

Abstract

The invention relates to an epoxy resin grouting material, in particular to a novel environment-friendly epoxy resin grouting material and a production method thereof.The novel environment-friendly epoxy resin grouting material comprises a component A and a component B. The component A comprises 100 parts of an epoxy resin main agent, 10-100 parts of an active diluent, a trace amount of a surface treating agent and other additives, and the component B comprises 20-40 parts of a curing agent. The formula of the epoxy resin grouting material is improved, the volatilization of the epoxy resin grouting material is greatly reduced, the toxicity before and after curing is reduced, the preparation method is improved, benzaldehyde and acetone are subjected to a condensation reaction to form the diluent, then the diluent is mixed with the resin main agent, and the epoxy resin grouting material is prepared. Heat release during mixing of benzaldehyde, acetone and epoxy resin is reduced, and volatilization of harmful substances is reduced.

Description

Technical Field

[0001] The invention relates to an epoxy resin grouting material, in particular to a novel environmentally friendly epoxy resin grouting material and a production method thereof. Background Art

[0002] Epoxy resin grouting material has the characteristics of high bonding strength, good heat resistance, high mechanical strength, excellent stability and small shrinkage after curing at room temperature. It is currently the most commonly used engineering reinforcement grouting material.

[0003] Epoxy resin itself has very high viscosity, and a certain amount of organic solvent is usually added to prepare the grouting fluid. Currently, the most widely used epoxy diluent is furfural-acetone system.

[0004] Furfural is highly toxic and volatile, causing great harm to construction workers and the environment. As an improvement, it has been proposed to use low-volatile, low-toxic solvents as diluents. However, the grouting materials prepared with low-volatile, low-toxic solvents, such as n-butanol and cyclohexanone, have a high initial viscosity. When poured into the gap, they have low penetration and poor pourability. Summary of the invention

[0005] One of the purposes of the present invention is to provide a novel environmentally friendly epoxy resin grouting material to solve the above technical problems.

[0006] A novel environmentally friendly epoxy resin grouting material comprises a component A and a component B, wherein the component A comprises 100 parts of an epoxy resin main agent, 10-100 parts of an active diluent, a trace amount of a surface treatment agent and other additives, and the component B comprises 20-40 parts of a curing agent, wherein the active diluent comprises a furfural substitute.

[0007] A further alternative to furfural is benzyl alcohol.

[0008] An alternative to furfural is benzaldehyde.

[0009] Furthermore, the active diluent also includes acetone.

[0010] Furthermore, the curing agent is a polymer modified amine.

[0011] Furthermore, it also includes a surfactant and a coupling agent.

[0012] The second object of the present invention is to provide a method for producing a novel environmentally friendly epoxy resin grouting material, comprising the following steps:

[0013] Step 1: Add a certain amount of acetone into a 100 ml three-necked flask equipped with a stirrer, a thermometer, and a dropping funnel;

[0014] Step 2, slowly drip the furfural substitute from the dropping funnel, and continue stirring for 30 minutes after dripping;

[0015] Step three, the solution obtained in step two is mixed with low-viscosity epoxy resin in proportion to obtain a novel low-viscosity furfural-free epoxy resin chemical grouting material.

[0016] Furthermore, in step 1, a catalyst is added, and the mixture is rapidly stirred (>650 r / min) at room temperature (20° C.).

[0017] The beneficial effects achieved by the present invention using the above formulation and method are as follows:

[0018] 1. The present invention improves the formula of epoxy resin grouting material, greatly reduces its volatilization, and reduces the toxicity before and after curing.

[0019] 2. By improving the preparation method, benzaldehyde and acetone are first allowed to condense to form a diluent, which is then mixed with the resin main agent to reduce the heat release when benzaldehyde, acetone and epoxy resin are mixed, thereby reducing the volatilization of harmful substances.

[0020] 3. The modified preparation of epoxy resin main agent and curing agent effectively reduces the viscosity of the grouting material with E2 type resin as raw material. The prepared epoxy resin grouting material has good groutability in the initial stage of regrouting, and after curing, it has strong adhesion, small shrinkage and high stability. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 The structure diagram of the modified bisphenol A epoxy resin of the present invention;

[0022] Figure 2 is the infrared spectrum of the epoxy resin main agent of the present invention;

[0023] Figure 3 This is a rat acute toxicity test diagram of the present invention;

[0024] Figure 4 This is a graph showing the change in contact angle between the slurry of the present invention and granite over time. DETAILED DESCRIPTION

[0025] The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all the embodiments; based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0026] In order to make the contents of the present invention more clearly understood, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the accompanying drawings in the embodiments of the present invention.

[0027] The present invention provides a novel environmentally friendly epoxy resin grouting material, comprising component A and component B, wherein component A comprises 100 parts of an epoxy resin main agent, 10-100 parts of an active diluent, a trace amount of a surface treatment agent and other additives, and component B comprises 20-40 parts of a curing agent, wherein the active diluent comprises a furfural substitute;

[0028] Embodiment 1,

[0029] In the present invention, the epoxy resin main agent is E1 type bisphenol A type epoxy resin,

[0030] Main technical indicators of E1 bisphenol A epoxy resin

[0031]

[0032] It should be noted that when selecting bisphenol A epoxy resin in the present invention, the priority indicators for comparison are adhesion, shrinkage and stability;

[0033] After determining the epoxy resin, it can be seen that its viscosity is 11000~14000mPa·s, which is relatively high. After modification, the structure of the modified bisphenol A epoxy resin is as follows: Figure 1 shown.

[0034] The greater the adhesion, the better; the smaller the shrinkage, the better; the higher the stability, the better.

[0035] The substitute for furfural is benzyl alcohol, which is less toxic and is a low-toxic solvent. It has less acute and chronic toxicity to the human body, is not prone to carcinogenic and mutagenic risks, and has relatively small hazards from skin contact and inhalation, which helps to improve the safety of the construction environment.

[0036] The active diluent also includes acetone, which reduces the initial viscosity of the system, facilitates stirring and mixing, and improves the uniformity of each component.

[0037] During the preparation, epoxy resin main agent, acetone and benzyl alcohol are mixed and stirred to obtain component A;

[0038] Then, component A and component B are mixed to obtain the epoxy resin grouting material of Example 1;

[0039] Embodiment 2,

[0040] In this example, the epoxy resin grouting material includes component A and component B, wherein component A includes 100 parts of epoxy resin main agent, 10-100 parts of active diluent, trace amounts of surface treatment agent and other additives, and component B is 20-40 parts of curing agent, wherein the active diluent includes furfural substitute and acetone, and the furfural substitute is benzaldehyde;

[0041] Benzaldehyde has low toxicity and is a low volatile organic compound (VOC), which poses little harm to the environment and human body.

[0042] First, benzaldehyde and acetone are mixed, and benzaldehyde and acetone undergo claisen condensation reaction. This reaction is related to the type and amount of catalyst, reaction temperature, and the ratio of reaction materials.

[0043] In this embodiment, the reaction temperature is room temperature (20°C);

[0044] Add a certain amount of acetone to a 100ml three-necked flask equipped with a stirrer, a thermometer, and a dropping funnel, and stir rapidly (>650r / min) at room temperature (20°C);

[0045] Slowly drip benzaldehyde from the dropping funnel, control the dripping speed so that it is finished within 30 minutes, and continue stirring for 30 minutes after the dripping is completed;

[0046] Wherein, acetone is 5 to 50 parts;

[0047] Benzaldehyde is 5 to 50 parts.

[0048] Preferably, the solution temperature does not exceed 30°C during the reaction;

[0049] The above reactants and low-viscosity epoxy resin are prepared in a certain proportion to obtain the epoxy resin grouting material of this embodiment.

[0050] Embodiment 3,

[0051] In this example, the epoxy resin grouting material includes component A and component B, wherein component A includes 100 parts of epoxy resin main agent, 10-100 parts of active diluent, trace amounts of surface treatment agent and other additives, and component B is 20-40 parts of curing agent, wherein the active diluent includes a furfural substitute;

[0052] The curing agent is a polymer modified amine. The structure and properties of the curing agent directly affect the application effect of the epoxy resin.

[0053] In this embodiment, a modified polymer primary amine with a long fatty chain is prepared as a curing agent;

[0054] First, a long aliphatic chain is introduced into a primary amine molecule through an amidation reaction to obtain a long aliphatic chain primary aminated product;

[0055] Add fatty acid (such as stearic acid) and ethylenediamine into the reactor in a molar ratio of 1:1.2;

[0056] The temperature was raised to 140°C, stirred and maintained for 6–8 hours, during which water was removed.

[0057] After the reaction is completed, the mixture is cooled to obtain a long fatty chain primary aminated product.

[0058] Then, the molecular weight of the primary amine is increased through polymerization reaction, thereby improving the performance of the curing agent;

[0059] Add long fatty chain primary amination product and epichlorohydrin into the reactor, control the molar ratio to 1:1, stir and react at 60-80°C for 4-6 hours, control the pH value to 8-10 to avoid side reactions, and remove unreacted products from the product by vacuum distillation to obtain a polymer primary amine curing agent.

[0060] The activity and quantity of the amino group can be changed by substituting the R' group, thereby regulating the reaction rate of the curing agent and the epoxy resin;

[0061] Preferably, the ratio of epoxy resin to curing agent is 4 to 6:1.

[0062] The composition of each component of epoxy resin is as follows:

[0063] Epoxy Grouting Material Formula

[0064]

[0065] The main properties of epoxy resin grouting materials are as follows:

[0066] Main properties of epoxy resin grouting materials

[0067]

[0068] Before curing, the epoxy resin grouting material was tested for harmful substances such as volatile organic compounds benzene, toluene + ethylbenzene + xylene, phenol, etc. according to the test method of JC066-2008 "Limits of Harmful Substances in Building Waterproof Coatings". The test results are shown in the following table;

[0069] Volatile organic compound test results

[0070]

[0071]

[0072] The solidified body of the epoxy resin grouting material after curing is subjected to an acute toxicity test on rats in accordance with GB / T21757-2008 "Acute Toxicity Classification Method for Acute Oral Toxicity Test of Chemicals" of the General Administration of Quality Supervision, Inspection and Quarantine of the People's Republic of China. After a single intragastric administration of the epoxy resin grouting material to rats, whether the test animals produce toxic reactions is observed, thereby evaluating the toxicity of the material;

[0073] like Figure 3 As shown, three SD rats were gavaged with epoxy resin grouting materials at a dose of 5000 mg / kg;

[0074] The animals were observed for 14 consecutive days, and their body weights were measured on the 7th and 13th days after administration. The rats were killed on the 14th day after administration for gross autopsy.

[0075] After the administration of the materials, the appearance and behavior, secretions and excretions of the animals in each group were normal, and no animals died. Body weight measurement: The body weights of the three rats showed an increasing trend at each time point after the administration of the materials. The test results are shown in the table below.

[0076] Body weight of rats at different time points after epoxy grouting

[0077]

[0078] On the 14th day after the test article was administered, sodium pentobarbital was injected intraperitoneally to induce deep anesthesia, the abdominal cavity was opened, the abdominal aorta was cut, and the animals were bled to death. Gross dissection and observation of the main organs and tissues showed no visible pathological changes;

[0079] Under the experimental conditions, the epoxy resin grouting material was orally administered to SD rats in a single acute toxicity test at 5000 mg / kg. All the animals survived and no obvious toxicity was observed. The LD50 of this test product is greater than 5000 mg / kg, and its toxicity is extremely low. It cannot be classified according to the GHS acute toxicity classification.

[0080] Embodiment 4,

[0081] The difference between this embodiment and embodiment 3 is that the other additives are surfactants and coupling agents;

[0082] After mixing the epoxy resin with the diluent, add the surfactant and coupling agent, control the temperature between 20–40°C, and stir at a low speed until evenly mixed.

[0083] Preferably, the amount of surfactant added is 0.5 parts to 2 parts;

[0084] The amount of coupling agent added is 0.5 parts to 2 parts.

[0085] The surface chemical performance indicators of epoxy grouting materials before and after modification are as follows:

[0086] Surface chemical properties of epoxy grouting materials before and after modification

[0087]

[0088]

[0089] The contact angle between the slurry and granite changes with time. Figure 4 As shown, it can be seen that the contact angle between the slurry and the granite decreases to 0 degrees in about 30 minutes, indicating that the epoxy grouting material completely wets the granite body and has excellent penetration ability and wettability.

[0090] Embodiment 5,

[0091] This embodiment is substantially the same as embodiment 2, except that the furfural substitute is benzyl alcohol.

[0092] When preparing the diluent of Agent A, benzyl alcohol and acetone are mixed in a certain proportion under stirring.

[0093] Add a catalyst to cause a condensation reaction between benzyl alcohol and acetone.

[0094] The temperature range is controlled according to the catalyst selected.

[0095] Preferably, the catalyst is sodium hydroxide, and the mixture is stirred rapidly (>650 r / min) at room temperature (20° C.).

[0096] After the reaction is completed, it is usually necessary to remove the catalyst and purify the product by methods such as acid neutralization or water washing.

[0097] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention shall be included in the protection scope of the present invention.

Claims

1. A new type of environmentally friendly epoxy resin grouting material, comprising component A and component B, wherein: Component A includes 100 parts of epoxy resin main agent, 10-100 parts of active diluent, trace amount of surface treatment agent and other additives, and component B includes 20-40 parts of curing agent, characterized in that the active diluent includes a furfural substitute.

2. A novel environmentally friendly epoxy resin grouting material according to claim 1, characterized in that: A furfural substitute is benzyl alcohol.

3. A novel environmentally friendly epoxy resin grouting material according to claim 1, characterized in that: A furfural substitute is benzaldehyde.

4. A novel environmentally friendly epoxy resin grouting material according to claim 1, characterized in that: The reactive diluent also includes acetone.

5. The novel environmentally friendly epoxy resin grouting material according to claim 1, characterized in that: The curing agent is a polymer modified amine 6. The novel environmentally friendly epoxy resin grouting material according to claim 1, characterized in that: Other additives include surfactants and coupling agents.

7. A method for producing a novel environmentally friendly epoxy resin grouting material, used for preparing the novel environmentally friendly epoxy resin grouting material according to any one of claims 1 to 8, characterized in that: The following steps are involved: Step 1: Add a certain amount of acetone into a 100 ml three-necked flask equipped with a stirrer, a thermometer, and a dropping funnel; Step 2, slowly drip the furfural substitute from the dropping funnel, and continue stirring for 30 minutes after dripping; Step three, the solution obtained in step two is mixed with low-viscosity epoxy resin in proportion to obtain a novel low-viscosity furfural-free epoxy resin chemical grouting material.

8. The method for producing a novel environmentally friendly epoxy resin grouting material according to claim 7, characterized in that: In step 1, a catalyst is also added to cause a condensation reaction between benzyl alcohol and acetone.

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