KR20000032569A - Process for producing one-component urethane waterproof composition - Google Patents

Abstract

PURPOSE: One-component urethane waterproof material compositions and process for producing the same are provided which are capable of removing water with ease and have an effect on shutting off water leakage by reacting with water, forming a polyurethane foam and filling up cracks. CONSTITUTION: A method for producing one-component urethane waterproof material compositions comprises the steps of (1) mixing a hydrophilic emulsifier and a polymerization inhibiting agent with a polyol(A) and removing moisture by conventional methods, (2) mixing with a reaction stabilizer, an excess amount of diisocyanate(B) to be above from 3.5 to 20% by weight of residual NCO after reaction, silicon oil and a reaction accelerator, (3)reacting at 65 to 90°C to be 3.5 to 20% by weight of residual NCO based on the total weight of the polyol(A) and the diisocyanate(B) and (4)mixing with the polymerization inhibiting agent. The composition is excellent in storage stability and convenient for use.

Description

Method for producing a one-component urethane index composition

The present invention relates to a method for preparing a one-component urethane index composition, in particular, a water-curable one-component index agent that has the effect of blocking water leakage by inflating the volume and expanding water at the same time as bubbles are generated by reaction with water. It relates to a method for preparing the composition.

Polyurethanes are generally obtained by the polyaddition reaction of diols and diisocyanates. Industrially, diisocyanates include toluene diisocyanate (TDI), methylene diphenyl diisocyanate (MDI), and hexamethylene di. Isocyanate (HDI) is used a lot, and as diol, poly (ethylene oxide), poly (propylene oxide), polyester glycol, etc. are used in addition to ethylene glycol, propylene glycol, 1,4-butanediol.

Polyurethanes can be produced in various physical properties, ranging from elastomers to hard plastics, depending on the type of diisocyanate and diol selected. In particular, excess isocyanates generate carbon dioxide when reacted with water or carboxylic acids. It also makes foams.

The present invention starts from the discovery that when such excess isocyanate reacts with water, bubbles are violently generated, and when bubbles are generated, the surface area is widened to adsorb liquid such as surrounding water and confine it in the bubbles.

In general, subway tunnels or large underground structures are grouted with concrete so that groundwater does not flow into them. If cracks occur, groundwater flows between the gaps. Therefore, the gap is physically filled with concrete or a polymeric sealing material, or the absorbent polyurethane foam composition is continuously injected into the gap to absorb and remove water.

However, since the urethane prepolymer prepared by diol and diisocyanate is poor in storage stability, a two-component type that generates polyurethane foam by reacting diol and diisocyanate directly at the site of use is commonly used.

However, the two-component type has poor workability, and it is not easy to continuously control the flow rate of the two components, diol and diisocyanate.

Thus, efforts have been made to prepare a one-component urethane index composition. For example, Japanese Patent Laid-Open No. JP-07025967 describes a one-component urethane index composition comprising a hydrophilic urethane prepolymer and an organic polyisocyanate. It has a high curing rate and absorbs water and has good shape retention in a swelled state, and there is no comment on storage stability.

Japanese Laid-Open Patent Publication JP-07062227 describes a urethane prepolymer composition containing polysiloxane, filler, calcium carbonate, talc, cement and the like, which has good curability and storage stability and has a shelf life of 6 months or more.

It is an object of the present invention to provide a method for preparing a one-part urethane index composition having good storage stability and ease of use.

The process for producing a one-component urethane index composition of the present invention comprises a first step of mixing a part of a hydrophilic emulsifier and a polymerization inhibitor requirement with a polyol (A) and dehydrating it according to a conventional method; Reaction stabilizer, excess diisocyanate (B), silicone oil and reaction accelerator to mix the residual NCO to 3.5 to 20% by weight after the reaction is mixed and the temperature is raised to 65 ~ 90 ℃, the total weight of (A) and (B) A second step of reacting the remaining NCO to 3.5 to 20% by weight based on the amount of NCO; The third step is to mix the remaining polymerization inhibitor.

Polyols (A) are those having 2 to 8 hydroxyl groups and diols are polyols of various structural formulas, including ethylene glycol, propylene glycol, poly (ethylene oxide), poly (propylene oxide), polyester glycol, or mixtures thereof. Can be used.

If water is contained in the polyol (A), it is reacted with the diisocyanate (B), so the water must be removed to 0.5% by weight, preferably 0.1% by weight or less before mixing with the diisocyanate.

Moisture removal is carried out by a conventional method such as heating or vacuum degassing, but it is more effective to blow dry air or nitrogen together with heating or vacuum degassing.

Hydrophilic emulsifiers can be used for both cation and anion. For example, DMPA or CX100 is used in an amount of 1 to 15% by weight based on the total weight of the polyol (A) and the diisocyanate (B).

As the reaction stabilizer, 0.01 to 1% by weight of benzoyl chloride is used based on the total weight of the polyol (A) and the diisocyanate (B).

The diisocyanate (B) uses toluene diisocyanate (TDI), methylene diphenyl diisocyanate (MDI), hexamethylene diisocyanate (HDI), or a mixture thereof, so that the remaining NCO group is 3.5 to 20% by weight after the reaction. Excess is used relative to the polyol (A).

The reaction is initiated by mixing and raising the temperature of the reaction stabilizer, diisocyanate (B), silicone oil and reaction promoter to a mixture of the polyol (A) and the hydrophilic emulsifier after the dehydration step.

The reaction accelerator uses 1-7% by weight of DMDEE (trade name: Jeffcat, manufactured by Huntsmann) based on the total weight of the polyol (A) and diisocyanate (B).

After the reaction starts, the remaining NCO groups are periodically measured and terminated when the remaining NCO groups are 3.5 to 20 wt% based on the total weight of the polyol (A) and the diisocyanate (B), and the remaining polymerization inhibitor is added after the completion of the reaction. .

As the polymerization inhibitor, phosphoric acid, formic acid, or MSA (methane sulfonic acid) is added, which prevents polymerization and improves shelf life, and has an effect of neutralizing the composition to neutrality.

The invention will be further clarified by the following examples.

<Example 1>

200 g of a polyol mixture of 150 g of H-4701, 10 g of H-2000, and 20 g of H-3021 [Kumho Chemical Co., Ltd.] is mixed with 3 g of CX100 with a hydrophilic emulsifier and 0.01 g of phosphoric acid with a polymerization inhibitor. Was removed and cooled to 50 ° C.

Next, after mixing 0.016 g of benzoyl chloride as a reaction stabilizer, 300 g of methylene diphenyl diisocyanate (MDI), 5 g of silicone oil (trade name: Silicone Surfactant 9475, manufactured by Pelron) and 2 g of a reaction accelerator (DMDEE) were mixed and the temperature was adjusted. The reaction was started at 75 DEG C and 2 g of DMDEE was added as a reaction accelerator.

The residual NCO was measured periodically to terminate the reaction when the residual NCO was 10.5 wt% based on the sum of the weights of the polyol mixture and the MDI, and 0.06 g of formic acid was added.

After the completion of the reaction, a dark brown composition was obtained, and when foamed in water, surface curing and complete curing were performed in 1 minute and 3 minutes, respectively, and the degree of foaming (= volume of resin after foaming / volume of resin before foaming) was 58 ±. was measured by the water absorption amount is 5 I was foamed composition per 1cm ³ 49cm ^3.

As a result of measuring the preservation period, the period of preservation without curing at room temperature was one year and June, and then gelation started slowly. When stored below 5 ° C, the gel did not gel for more than 2 years.

<Example 2>

It was carried out under the same conditions as in Example 1, except that a mixture of 150 g of H-4701 and 50 g of H-3021 (above Kumho Chemical Co., Ltd.) and 0.015 g of a polymerization inhibitor was used as a polyol. The results are shown in Table 1.

<Example 3>

It was carried out under the same conditions as in Example 1, except that a mixture of 30 g of H-3021, 20 g of H-280 and 150 g of H-4701 (above Kumho Chemical Co., Ltd.) and 0.015 g of polymerization inhibitor was used as a polyol. . The results are shown in Table 1.

<Example 4>

A polyol was used under the same conditions as in Example 1, except that 150 g of H-4701 and 50 g of H-280 [more than Kumho Chemical Co., Ltd.] were used and 0.015 g was used as a polymerization inhibitor. The results are shown in Table 1.

Item Example 2 Example 3 Example 4 Composition Diols or polyols H-4701 150gH-3021 50g H-3021 30gH-280 20gH-4701 150g H-4701 150gH-280 50g Diisocyanate MDI 300g Left Left Hydrophilic emulsifiers DMPA 40g Left Left Reaction stabilizer Benzoyl chloride 0.016 g Left Left Reaction accelerator DMDEE 4g Left Left Silicone oil 9415 5g Left Left Polymerization inhibitor 0.015 g of phosphoric acid Left Left Foam Properties Surface hardening time (minutes) One One One Internal hardening time (minutes) 3 3 3 Firing degree 50 ± 5 55 ± 5 52 ± 5 Water absorption (cm ³ / composition 1cm ³ ) 46 ± 5 48 ± 5 46 ± 5 Zhejiang 1 year June 1 year June 1 year June

Since there is no commercially available one-part index agent, it cannot be compared, but it can absorb 40 times or more of the volume of the composition before foaming, and the conventional one-part polyurethane foam composition has a shelf life of 6 to 9 months or less. Compared with the composition prepared according to the present invention, it can be seen that the shelf life is very long.

As it is a one-component type, it can be easily removed from leaking underground structures or other places where it is necessary to remove water. In addition, the polyurethane foam is formed by reacting with water, so that the volume is increased, there is also the effect of blocking the leak to fill the cracks.

Claims (5)

Mixing the hydrophilic emulsifier and the polymerization inhibitor into the polyol (A) and removing water according to a conventional method; Reaction stabilizer, excess diisocyanate (B), silicone oil and reaction promoter to mix the residual NCO to 3.5-20% by weight or more, and raise the temperature to 65 ~ 90 ℃ polyol (A) and diisocyanate (B Reacting the remaining NCO to 3.5 to 20% by weight based on the weight of the c); A method for producing a one-part urethane index composition comprising a third step of mixing a polymerization inhibitor. The method for producing a one-part urethane index composition according to claim 1, wherein 1 to 15% by weight of DMPA or CX100 is used as the hydrophilic emulsifier based on the total weight of the polyol (A) and the diisocyanate (B). . The method for producing a one-part urethane index composition according to claim 1, wherein 0.01 to 1% by weight of benzoyl chloride is used as a reaction stabilizer based on the total weight of the polyol (A) and the diisocyanate (B). The method according to claim 1, wherein 1 to 5% by weight of DMDEE (trade name: JEFFCAT, manufactured by Huntsmann) is used as a reaction accelerator based on the total weight of the polyol (A) and the diisocyanate (B). The manufacturing method of a urethane index agent composition. The method of claim 1, wherein the reaction accelerator is mixed in a ratio of 2 to 8: 8 to 2 in the second and third stages.