TWI402241B - Waterproof geopolymer and method for forming the same - Google Patents

Description

Waterproof inorganic polymer and preparation method thereof

The present invention relates to an inorganic polymer and a process for the preparation thereof, and in particular to a water-repellent inorganic polymer and a process for the preparation thereof.

A geopolymer is an amorphous or semi-crystalline material with excellent physical and chemical properties such as good fire resistance, chemical resistance, short molding time, low temperature preparation, Low CO ₂ emissions, etc. Inorganic polymers can be applied to building materials and structural engineering. They have great potential for development and have the opportunity to replace cement concrete and become the raw material for building materials and structural engineering.

However, inorganic polymers are porous materials that are susceptible to physical effects and scale. Moisture or salt in the air may invade the inorganic polymer, causing the whiteness of the inorganic polymer. In addition, the moisture of the intrusion will also cause problems such as deterioration of materials and corrosion of internal building materials such as steel bars.

Therefore, the water-repellent inorganic polymer can assist the industry in the construction materials, and it is urgent to have an inorganic polymer having waterproof properties and a method for preparing the same.

The present invention provides a method for forming a water-repellent inorganic polymer, comprising providing an alkaline tantalate modifying solution, and adding an aluminosilicate mineral to an alkaline tantalate modifying solution to form a water-repellent inorganic polymer, wherein Aluminate minerals and alkaline bismuth The weight ratio of the acid-modified solution is between about 0.5 and 1.5.

The water-repellent inorganic polymer of the embodiment of the invention comprises an inorganic polymer comprising an aluminosilicate mineral, and the interior of the inorganic polymer comprises a plurality of first pores, and the surface of the inorganic polymer comprises a plurality of second pores, and The bismuth acid waterproof material substantially fills the first pore and the second pore.

The above and other objects, features and advantages of the present invention will become more <RTIgt;

In the embodiment of the present invention, a basic tannin modified solution is introduced into the inorganic polymer precursor to carry out polymerization of the inorganic polymer. By introducing an alkaline tantalum acid upgrading solution, the formed inorganic polymer can have a lower porosity and enhance the waterproof property of the inorganic polymer.

The method for forming a water-repellent inorganic polymer according to an embodiment of the present invention comprises forming an aluminosilicate mineral by adding it to an alkaline tantalate-based reforming solution. Aluminosilicate minerals suitable for the present invention include any mineral, solid, or waste that can dissolve strontium ions or aluminum ions in an alkaline solution. Bridging can occur between colloidal particles containing cerium ions and/or aluminum ions dissolved in an alkaline solution. After dehydration drying, an inorganic polymer having strength can be formed. Aluminosilicate minerals suitable for the present invention are, for example, kaolin, metakaolin, bentonite, coal ash slag, steelmaking slag, aggregate, sand, or a combination of the foregoing. Among them, metakaolin can be obtained by calcining kaolin, and the calcination temperature is about 650. Between ° C and 800 ° C, preferably about 700 ° C. The surface of the metakaolin and the aluminum will be more readily precipitated under alkaline conditions to provide the colloid required for the polymerization of the inorganic polymer.

The alkaline solution added in the embodiment of the present invention can dissolve the cerium ions and aluminum ions in the aluminosilicate mineral, and the ceric acid modifying agent is copolymerized with them to form a water-repellent inorganic polymer. In one embodiment, the weight ratio of the aluminosilicate mineral to the alkaline phthalate modifying solution is between about 1.0 and 2.0. In another embodiment, the weight ratio of the aluminosilicate mineral to the alkaline phthalate modifying solution is between about 0.8 and 1.5. In yet another embodiment, the weight ratio of the aluminosilicate mineral to the alkaline phthalate modifying solution is between about 1.2 and 1.8. The alkaline phthalate modification solution of the embodiment of the invention comprises adding a phthalic acid modifier to an alkaline solution.

The bismuth acid modifiers suitable for the present invention include organic oxime modifiers such as methyl decoxide, oxime resin, decane, organic hydrazine emulsion, or combinations of the foregoing. In one embodiment, the weight ratio of the phthalic acid modifier to the aluminosilicate mineral is between about 0.02 and about 0.2. In another embodiment, the weight ratio of the phthalic acid modifier to the aluminosilicate mineral is between about 0.04 and about 0.1. In yet another embodiment, the weight ratio of the phthalic acid modifier to the aluminosilicate mineral is between about 0.05 and 0.08.

The alkaline solution suitable for the present invention includes an aqueous solution of sodium hydroxide, potassium hydroxide or the like, or a combination of the foregoing. In one embodiment, the concentration of sodium hydroxide or potassium hydroxide in the alkaline solution is between about 0.1 N and 10 N. In another embodiment, the concentration of sodium hydroxide or potassium hydroxide in the alkaline solution is between about 0.5 N and 5 N. In yet another embodiment, the sodium hydroxide of the alkaline solution or The concentration of potassium hydroxide is between about 1 N and 3 N.

In one embodiment, the addition of a citrate to the alkaline citrate modifier is further included. Citrate provides enough ions to promote cementation between the colloids. Suitable phthalates include sodium citrate, potassium citrate, or combinations of the foregoing. In one embodiment, the SiO ₂ /M ₂ O modulus ratio of the citrate to the alkaline solution is from 0.75 to 1.0, wherein M is sodium or potassium. In another embodiment, the SiO ₂ /M ₂ O modulus ratio is from 1.0 to 1.25. In yet another embodiment, the SiO ₂ /M ₂ O modulus ratio of the citrate to the alkaline solution is between 1.25 and 1.5. Wherein, SiO ₂ / M ₂ O in the modulo M ₂ O In terms of Na ₂ O, for example, refers to the concentration of sodium molar solution of sodium silicon of silicon / silicon oxide, and a solution of sodium sodium alkaline solution The molar concentration (ie, the molar concentration of strontium: the molar concentration of sodium in the sodium citrate solution + the molar concentration of sodium in the alkaline solution).

In one embodiment, a mixture of the aluminosilicate mineral and the alkaline phthalate modifying solution is further added to the mold and allowed to stand for curing molding, for example, between about 10 ° C and 40 ° C. In addition, a mixture of the aluminosilicate mineral and the alkaline phthalate modification solution may be oscillated and degassed, for example, a mechanical oscillator may be used. After shock and degassing, the uniformity and structural integrity of the colloid can be maintained.

The water-repellent inorganic polymer of the embodiment of the present invention comprises an aluminosilicate mineral having a plurality of first pores in the water-repellent inorganic polymer and a plurality of second pores on the surface of the water-repellent inorganic polymer. Wherein, the first pores and the second pores are substantially filled with the enamel waterproof material. The enamel waterproof material is obtained by reacting an aluminosilicate mineral with an alkaline phthalate modification solution. The water-repellent inorganic polymer of the embodiment of the invention is formed by copolymerizing an aluminosilicate mineral with an alkaline tantalum acid upgrading solution, and the tantalum-based waterproof material can substantially fill the pores in the inorganic polymer, thereby effectively avoiding Water vapor enters the inorganic polymer. In one embodiment, the weight ratio of the water-repellent inorganic polymer soaked in water for 24 hours to the amount of water absorbed by the general inorganic polymer in water for 24 hours is less than 0.1. In one embodiment, the contact angle between the water-repellent inorganic polymer and the water droplets is greater than about 75° and has a high hydrophobicity. In one embodiment, the strength of the water-repellent inorganic polymer is greater than about 550 kgf/cm ² . In one embodiment, the strength of the water-repellent inorganic polymer is about 120% of the inorganic polymer excluding the enamel waterproof material.

Hereinafter, the flow is substantially the same for different embodiments, and the change of the ratio is the main parameter. Therefore, the preferred embodiment of the test results is listed to further illustrate the embodiment of the present invention. A flow chart of a method for forming a water-repellent inorganic polymer according to an embodiment of the present invention is shown in Fig. 1, for example.

[Examples] Example 1

Kaolinite was placed in a high temperature furnace at 700 ° C for firing. The temperature was maintained for 3 hours to dehydrogenate the kaolin and transform it into an amorphous metakaolin. Metakaolin will be used as a source of aluminosilicate minerals.

Next, an alkaline tantalate modifying solution was prepared. 856ml, 4N NaOH solution and 6052g sodium citrate were uniformly adjusted into a SiO ₂ /M ₂ O ratio of 1.25 polymerization precursor, 720 grams of precursor was taken out and 80 grams of bismuth acid modifier was added to uniformly mix to form a base. A bismuth acid modification solution.

Next, 800 grams of metakaolin was added to 800 grams of the alkaline phthalate modification solution and mechanically stirred for 15 minutes. After stirring, the mixture was poured into a mold and shaken for 10 minutes. Finally, the mold is sealed and cured at room temperature. After the colloid hardening is formed, the mold is released, and the CNS3763 (class No. A2047) is tested and hydrophobic. Sex test. Among them, the hydrophobicity test is to drop water droplets on the surface of the inorganic polymer, and measure the contact angle between the water droplets and the surface of the inorganic polymer. The test results are summarized in Table 1 as follows:

The experimental results show that the water-repellent inorganic polymer of the examples of the present invention can be tested by CNS3763 (class No. A2047) and its strength is higher than that of general inorganic polymers. The contact angle of the water-repellent inorganic polymer with water droplets of the embodiment of the present invention is as high as 79°, indicating that it has excellent hydrophobicity.

Hereinafter, the preparation process and test results of other embodiments of the present invention are listed.

Example 2

Kaolinite was placed in a high temperature furnace at 700 ° C for firing. Holding temperature The kaolin was dehydrogenated for 3 hours to be converted into an amorphous metakaolin. Metakaolin will be used as a source of aluminosilicate minerals.

Then, different ratios of bismuth acid modifiers were adjusted to prepare an alkaline phthalate modification solution. 856 ml of a 4 N NaOH solution, 6052 g of sodium citrate, and 20 g of a ruthenium acid modifier were uniformly mixed to form an alkaline tantalate modifying solution.

Next, 800 grams of metakaolin was added to about 800 grams of the alkaline phthalate modification solution and mechanically stirred for 15 minutes. After stirring, the mixture was poured into a mold and shaken for 10 minutes. Finally, the mold is sealed and cured at room temperature. After the colloid hardening is formed, the mold is released, and the CNS3763 (class No. A2047) test and the hydrophobicity test are performed. The test results are summarized in Table 2 as follows:

Example 3

Kaolinite was placed in a high temperature furnace at 700 ° C for firing. Holding temperature The kaolin was dehydrogenated for 3 hours to be converted into an amorphous metakaolin. Metakaolin will be used as a source of aluminosilicate minerals.

Adjust the NaOH solution at different concentrations. 856 ml, 2N NaOH solution, 6052 g of sodium citrate, and 80 g of bismuth acid modifier were uniformly mixed to form an alkaline phthalate modification solution.

Next, 800 grams of metakaolin was added to about 800 grams of the alkaline phthalate modification solution and mechanically stirred for 15 minutes. After stirring, the mixture was poured into a mold and shaken for 10 minutes. Finally, the mold is sealed and cured at room temperature. After the colloid hardening is formed, the mold is released, and the CNS3763 (class No. A2047) test and the hydrophobicity test are performed. The test results are summarized in Table 3 as follows:

Although the invention has been disclosed above in several preferred embodiments, it is not The scope of the present invention is intended to be limited to the scope of the invention, and the scope of the present invention is intended to be included in the scope of the invention. The definition is final.

Fig. 1 is a flow chart showing a method of forming a water-repellent inorganic polymer according to an embodiment of the present invention.

Claims (16)

A method for forming a water-repellent inorganic polymer, comprising: providing an alkaline bismuth acid modifying solution, wherein the alkaline phthalic acid modifying solution comprises adding a bismuth acid modifying agent to an alkaline solution, The bismuth acid modifier comprises an organic hydrazine modifier comprising methyl decoxide, hydrazine resin, decane, organic hydrazine emulsion, or a combination thereof, and the alkaline solution comprises sodium hydroxide And potassium hydroxide, or a combination thereof; and adding an aluminosilicate mineral to the alkaline tantalate modifying solution to form a water-repellent inorganic polymer, wherein the aluminosilicate mineral and the alkaline The weight ratio of the bismuth acid modifying solution is between about 0.5 and 1.5. The method for forming a water-repellent inorganic polymer according to claim 1, wherein the aluminosilicate mineral comprises kaolin, metakaolin, bentonite, coal ash slag, steelmaking slag, aggregate, sand, or the foregoing combination. The method for forming a water-repellent inorganic polymer according to claim 1, wherein a weight ratio of the bismuth acid modifier to the aluminosilicate mineral is between about 0.02 and 0.2. The method for forming a water-repellent inorganic polymer according to claim 1, further comprising adding a monocaprate to the alkaline phthalate modification solution. The method for forming a water-repellent inorganic polymer according to claim 4, wherein the phthalate salt comprises sodium citrate, potassium citrate, or a combination thereof. The method for forming a water-repellent inorganic polymer according to claim 4, wherein a ratio of SiO ₂ /M ₂ O of the ceric acid salt to the alkaline solution is between about 0.75 and 1.5, wherein M is sodium. Or potassium. Formation of a water-repellent inorganic polymer as described in claim 1 The method further comprises: adding a mixture of the aluminosilicate mineral and the alkaline phthalic acid modification solution to a mold; and mixing the aluminosilicate mineral with the alkaline phthalic acid modification solution Maintain at a temperature. The method for forming a water-repellent inorganic polymer according to claim 7, wherein the temperature is between about 10 and 40 °C. The method for forming a water-repellent inorganic polymer according to claim 7, further comprising oscillating and degassing the mixture of the aluminosilicate mineral and the alkaline phthalic acid modification solution. A water-repellent inorganic polymer comprising: an inorganic polymer comprising an aluminosilicate mineral, the interior of the inorganic polymer comprising a plurality of first pores, and the surface of the inorganic polymer comprising a plurality of second pores; a enamel waterproof material substantially filling the first pores and the second pores, wherein the enamel waterproof material is obtained by reacting the aluminosilicate mineral with an alkaline bismuth acid upgrading solution, the alkali The bismuth citrate modification solution comprises a bismuth acid modifier and an alkaline solution, and the bismuth modifier comprises an organic hydrazine modifier, and the hydrazine modifier comprises methyl hydroxide and hydrazine resin. A decane, an organic hydrazine emulsion, or a combination of the foregoing, and the alkaline solution includes sodium hydroxide, potassium hydroxide, or a combination thereof. The water-repellent inorganic polymer according to claim 10, wherein the aluminosilicate mineral comprises kaolin, metakaolin, bentonite, coal ash slag, steelmaking slag, aggregate, sand, or a combination thereof. The water-repellent inorganic polymer according to claim 10, wherein the alkaline phthalate modification solution further comprises a bismuth citrate. The water-repellent inorganic polymer of claim 12, wherein the bismuth salt comprises sodium citrate, potassium citrate, or a combination thereof. The water-repellent inorganic polymer according to claim 10, wherein a weight ratio of the water-absorbing amount of the water-repellent inorganic polymer immersed in water to the water absorption amount of the inorganic polymer not including the enamel waterproof material immersed in water is less than About 0.1, wherein the inorganic polymer excluding the enamel waterproof material comprises an aluminosilicate mineral. The water-repellent inorganic polymer according to claim 10, wherein a contact angle between the water-repellent inorganic polymer and water droplets is about 75°. The waterproof inorganic polymer according to claim 10, wherein the waterproof inorganic polymer has a strength of about 120% of an inorganic polymer excluding the phthalic acid waterproof material, wherein the enamel waterproofing is not included The inorganic polymer of the material includes an aluminosilicate mineral.