TW201512094A - Manufacturing method for chemical modification of a delaminated mica by sol gel hydrolytic condensation - Google Patents

Abstract

The present invention relates to a manufacturing method, taking advantage of the characteristics of a highly ion-exchanged mica capable of being fully dispersed in an acid solution, for chemical modification of the mica by a sol gel method. An ion exchange step is conducted by mixing mica powders and a basic solution under high temperature and high pressure; the ion-exchanged mica is filtered, collected and cleaned with deionized water and then put into a deionized aqueous solution; by adjusting the pH to a value below 6 the mica is delaminated and fully dispersed in the aqueous solution which is in a transparent state; a sol-gel reaction is performed directly in the mica aqueous solution to intercalate the mica with organic molecules, and after completion of the sol-gel reaction adjust the pH of the reactants to a value over 7, the organically surface-modified and intercalated mica is precipitated, filtered, cleaned, and finally dried to obtain the final products. The present invention, using the mica manufactured by mixing an acid and a basic solution under high temperature and high pressure, and capable of being delaminated and fully dispersed in an aqueous solution of which the pH value is below 6, enhances the organic surface-modification and intercalation of the mica by the sol gel method, different market applications can be targeted when the surface and interlays of the mica are chemically modified by compounds having different functional groups, thereby increasing the market applicability and competitiveness of the mica.

Description

Preparation method of stripping mica using sol-gel hydrolysis condensation to complete chemical modification

The invention relates to a method for preparing a chemically modified mica, in particular to a method for preparing a mica chemical modification by using a sol-gel hydrolysis condensation method after a highly ion-substituted mica is stripped in an acidic solution and completely dispersed.

Many literatures and studies have pointed out that the use of hydrothermal method or molten salt method to intercalate cations of mica can cause the bonding force between mica layers to be weakened. Generally, lithium nitrate or sodium hydroxide is used as an ion displacer. Lithium nitrate is often used because of its high price, high ion exchange temperature of lithium nitrate and mica, and long reaction time. The reaction is relatively fast and the price of sodium hydroxide is relatively low.

Taiwan Invention Patent Publication No. I312338 "A method for preparing mica which can be swollen in acid" discloses that an alkaline solution of sodium hydroxide and lithium hydroxide is used in an amount of 80% by weight or more, and other alkaline substances of 20% by weight or less are used under normal atmospheric pressure. Mica is ion-diffused to obtain a swellable mica that can be used in acid. However, most of the mica obtained by the conventional patent has not undergone organic modification, and has poor affinity with common organic substances, and mica has a problem of poor dispersion when applied.

The inventors of the present invention have invented a method for preparing a stripped mica using a sol-gel hydrolysis condensation to complete chemical modification, in view of the lack of the prior art, and the mica manufactured by the preparation method of the present invention utilizes It has the characteristics of peelable layer and complete dispersion under acidic aqueous solution. The sol-gel method is used to chemistry between mica interlayer and surface directly under acidic environment. Modification, chemical modification process is convenient and simple, and it is helpful for delamination and chemically modified mica in the market and its versatility.

The main object of the present invention is to provide a mica which is simple in process and which can be peeled off and chemically modified.

In order to achieve the above object of the present invention, the present invention provides a method for preparing a delaminated mica using a sol-gel hydrolysis condensation to complete chemical modification, comprising the following steps: (a) a raw material mixing step: a powdery mica and a metal alkaline solvent Adding together in a pressure cooker, wherein the powdery mica is in a weight ratio of the metal alkaline solvent of 5 to 95%; (b) a pressure heating reaction step: the powdered mica and the metal alkaline solvent are contained The pressure cooker is heated and stirred to 110 ° C ~ 280 ° C, and the boiler pressure system of the pressure cooker is 100 psi to 1000 psi, and the ion exchange time of the powdery mica and the metal alkaline solvent is 30 minutes to 24 hours; a filtration washing step: the mica after the completion of the step (b) is filtered, and the mica is directly rinsed with deionized water to remove excess metal alkaline solvent; (d) acidification dispersion step: after step (c) is completed The mica is added to the deionized water solution of 1 to 50 times the weight of the mica, and directly added hydrochloric acid, nitric acid, acetic acid, sulfuric acid or other acidic solvent which can be used as a sol-gel catalyst to adjust the pH to less than PH. After 6 , at this time, the mica system is completely dispersed in the deionized water solution and exhibits a completely transparent state; (e) a sol-gel reaction step: the pH is continuously adjusted to pH 2, and then the compound which is pre-performed by the sol-gel reaction is slowly added. The weight ratio is 1~200%, vigorous stirring for 30 minutes~24 hours; (f) acid-base neutralization and precipitation step: the pH value of the reaction solvent after completion of step (e) is adjusted to about pH7~PH8, and will be peeled off and completed. Chemically modified mica precipitated; (g) product drying collection step: filtering and collecting the mica precipitated in the solid after the step (f), and washing the solid mica with deionized water and alcohol, and solidifying the solid mica The body-shaped mica is dried at 100 ° C to obtain a chemically modified mica product.

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

10‧‧‧Preparation method

101~107‧‧‧Steps

Fig. 1 is a flow chart showing the preparation method of the delaminated mica of the present invention using sol-gel hydrolysis condensation to complete chemical modification.

Referring to Fig. 1 of the present invention, the delamination mica of the present invention is prepared by the hydrolytic hydrolysis of a sol gel to complete the chemical modification, and includes the steps (101) to (107), respectively, which are described below. The step (101) is a raw material mixing step, and the step (101) is to add powdered mica together with a metal alkaline solvent in a pressure cooker, wherein the powdery mica is in a metal alkaline solvent in a weight ratio of 5 to 95%. In the step (101), the powdered mica, sodium hydroxide and lithium hydroxide are mixed into the pressure cooker together with the alkaline solvent, and the weight ratio of the mica to the alkaline solvent mixed with sodium hydroxide and lithium hydroxide is 5 to 95. %.

Specific examples of the metal alkaline solvent may be lithium hydroxide, sodium hydroxide, potassium hydroxide, barium hydroxide, barium hydroxide, barium hydroxide or a mixture thereof. The configuration of the metal alkaline solvent is, for example, a percentage by weight, wherein the metal alkaline solvent is 5% to 95% by weight based on water. The mica is muscovite, sericite, colored mica, fluoromica or pyrophyllite.

Step (102) is a pressure heating reaction step, and step (102) heats the pressure cooker containing powdered mica and metal alkaline solvent to 110 ° C to 280 ° C, and the pressure cooker is 100 psi to 1000 psi. And the ion exchange time of the powdery mica and the metal alkaline solvent is 30 minutes to 24 hours. When step (101) is completed, step (102) is performed, in step (102) In the pressure cooker containing (powdered) mica and metal alkaline solvent, heat and stir to 110 ° C ~ 280 ° C, and the pressure of the pressure cooker boiler should be maintained at 100 psi ~ 1000 psi, at this time in the pressure cooker (powdered) mica and The metal alkaline solvent is ion-exchanged, and the ion exchange time is 30 minutes to 24 hours.

The pressure cooker can adopt a pressure axe resistant to strong acid and alkali, or a pressure cooker resistant to strong acid and alkali. The pressurizing step of step (102) can be accomplished in the pressure axe or the pressure cooker.

Step (103) is a filtration washing step, and step (103) is to complete the mica filtration after the step (102), and directly rinse the mica with deionized water to remove excess metal alkaline solvent. In step (103), after the ion exchange time is ended, the mica is filtered and the mica is directly washed with deionized water to remove the metal alkaline solvent remaining in the mica. Furthermore, step (103) can perform solid-liquid separation by suction filtration to perform filtration and dehydration of mica.

Step (104) is an acidification dispersion step, and step (104) is to add mica after completion of step (103) to a deionized water solution having a weight of 1 to 50 times of mica, and directly add hydrochloric acid, nitric acid, acetic acid, sulfuric acid or the like as The acidic solvent of the sol-gel catalyst adjusts the pH to less than PH 6 at which time the mica is completely dispersed in the deionized aqueous solution and is in a completely transparent state. In the step (104), the mica which has been subjected to the filtration cleaning is added to a deionized water solution having a weight of 1 to 50 times that of the mica, and directly added, for example, nitric acid, as a sol-gel catalyst for adjusting the pH to Less than PH 6, when the pH is adjusted to be less than PH 6, the mica at this time is completely dispersed in the deionized water solution and exhibits a completely transparent state.

Step (105) is a sol-gel reaction step, and step (105) is to continuously adjust the pH to PH 2, and slowly add the compound to the sol-gel reaction in a weight ratio of 1 to 200%, and vigorously stir for 30 minutes to 24 hours. hour. In the step (105), after the pH of the step (104) is continuously adjusted to 2, for example, 3-aminopropyltrimethoxysilane is slowly added to carry out a sol-gel reaction, 3-amino group. The compound ratio of propyltrimethoxysilane is from 1 to 200% by weight and vigorously stirred for 30 minutes to 24 hours.

The compound used in the step (105) may be selected from a decane compound or a compound which can undergo a hydrolysis condensation reaction with the mica.

The step (106) is an acid-base neutralization precipitation step, and the step (106) is to adjust the pH of the reaction solvent after the completion of the step (105) to about pH 7 to pH 8, and to separate and complete the chemically modified mica. In the step (106), the pH of the reaction solvent after the completion of the step (105) is adjusted to a pH of about pH 7 to pH 8, and the chemically modified mica is separated and precipitated.

Step (107) is a product drying collection step, and step (107) is a filtration of the solid methane precipitated after the step (106), and the solid mica is washed with deionized water and alcohol, and the solid mica is 100. The chemically modified mica product is obtained after drying at °C. In the step (107), the mica in a solid form is collected by filtration, and the solid mica is washed with deionized water and alcohol, and the solid mica is dried at 100 ° C, and dried to obtain a chemical change. Quality mica product.

The mica obtained by the present invention is chemically modified, and the mica has a functional group compatible with the resin after the chemical modification, and the specific surface area of the mica is increased after the delamination, and the chemical transformation of the delamination obtained by the present invention is changed. The mica is applicable to the filling of thermoplastic and thermosetting resins such as polyester, epoxy, PBT, polyamide, carbonate, etc., and can greatly improve the mechanical strength and electrical properties of the plastic, which is a significant improvement of the present invention.

While the present invention has been described in its preferred embodiments, the present invention is not intended to limit the invention, and the present invention may be modified and modified without departing from the spirit and scope of the invention. The scope of protection is defined by the scope of the patent application attached Subject to it.

10‧‧‧Preparation method

101~107‧‧‧Steps

Claims (10)

A method for preparing a stripped mica using sol-gel hydrolysis condensation to complete chemical modification comprises the following steps: (a) a raw material mixing step: adding powdered mica together with a metal alkaline solvent to a pressure cooker, wherein the powdery Mica in the metal alkaline solvent in a weight ratio of 5 to 95%; (b) pressure heating reaction step: the pressure cooker containing the powdery mica and the metal alkaline solvent is heated and stirred to 110 ° C ~ 280 ° C And the boiler pressure system of the pressure cooker is 100 psi to 1000 psi, and the ion exchange time of the powdery mica and the metal alkaline solvent is 30 minutes to 24 hours; (c) the filtration cleaning step: the step (b) is completed. The mica is filtered, and the mica is directly rinsed with deionized water to remove excess metal alkaline solvent; (d) acidification dispersion step: adding the mica after the completion of step (c) to the mica weight 1 to 50 Double the deionized water solution, and directly add hydrochloric acid, nitric acid, acetic acid, sulfuric acid or other acidic solvent which can be used as a sol-gel catalyst, and adjust the pH to less than PH 6 , at which time the mica system is completely dispersed. from In the aqueous solution, it is completely transparent; (e) Sol-gel reaction step: the pH value is continuously adjusted to PH 2, and the weight ratio of the compound which is pre-performed to the sol-gel reaction is slowly added, and the weight ratio is 1 to 200%, and the stirring is vigorously performed for 30 minutes to 24 hours. (f) acid-base neutralization precipitation step: adjusting the pH of the reaction solvent after completion of step (e) to about pH 7 to pH 8, and separating and completing the chemically modified mica; (g) product Drying and collecting step: collecting and collecting the mica in a solid state after the step (f), and washing the solid mica with deionized water and alcohol, and drying the solid mica at 100 ° C to obtain a chemical modification Mica product. The preparation method according to claim 1, wherein the mica of the step (a) is muscovite, sericite, colored mica, fluoromica or pyrophyllite. The preparation method according to claim 1, wherein the metal alkaline solvent of the step (a) is lithium hydroxide, sodium hydroxide, potassium hydroxide, barium hydroxide, barium hydroxide or barium hydroxide. Or a mixture thereof. The preparation method of claim 1, wherein the metal alkaline solvent of the step (a) is disposed in a percentage by weight, wherein the metal alkaline solvent is 5% to 95% by weight to water. . The preparation method according to claim 1, wherein the pressurizing step of the step (b) is carried out in a pressure axe or a pressure cooker resistant to strong acid and alkali. The preparation method according to the first aspect of the invention, wherein the step (c) is performing solid-liquid separation by suction filtration to perform filtration and dehydration of the mica. The preparation method according to claim 1, wherein the acidifying and dispersing step of the step (d) is carried out in water or another solvent which can be subjected to a sol-gel reaction. The preparation method according to the first aspect of the invention, wherein the sol-gel reaction step of the step (e) adjusts the pH of the acid used, which is hydrochloric acid, nitric acid, acetic acid, sulfuric acid or the like as a sol-gel method. The acidic solvent of the catalyst. The preparation method according to claim 1, wherein the compound used in the step (g) is a decane compound or a compound which can undergo a hydrolysis condensation reaction with the mica. The preparation method according to claim 1, wherein the chemical modification of the step (a) to the step (g) is carried out in a hydrolysis condensation reaction.