TWI270529B - Method for producing nano silicate plate - Google Patents

Abstract

A method for producing a nano silicate plate comprises performing a polymerization reaction on polyoxyalkylene amine, p-cresol, and formaldehyde to obtain a linear amine terminal-Mannich oligomer (AMO) intercalating agent, and using a substitution reaction to directly exfoliate clay. After being added with a hydroxide or chloride aqueous solution of alkaline metal or alkaline earth metal, ethanol, water, and an organic solvent, the resulting reaction solution was subjected to separation procedures (including filtration, conditioned motionless for separation, etc.) to obtain a layered nano silicate plate.

Description

1270529 骑 议 遽 灭 灭 灭 灭 灭 灭 灭 灭 灭 灭 灭 灭 灭 灭 灭 灭 灭 灭 灭 灭 灭 灭 灭 灭 灭 灭 灭 灭 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 A method for producing a directly delaminated nanosheet by a Mannesamine polymer intercalating agent. [Prior Art] Oxide layered inorganic clay has been used in the past for the reinforcing material of catalyst and polymer materials, which can loosen the clay interlayer through the intercalating reaction of the organic quaternary ammonium salt, and the interlayer distance is about For 10~20A. The loose interlayer allows the monomer to enter and exit, and then obtains an effluent organic/inorganic nano-polymer composite material through polymerization, and the material can be used as a reinforcing material for the polymer material to improve the polymer material. Thermal properties, mechanical properties, gas barrier properties and flame resistance. Organic/inorganic nano-polymer composites are considered to be important materials in the new century. The development and application of such materials is an extremely important issue for academics and industry. In recent years, there have been many publications and patents in this area. For example, TJ Pinnavaia (Michigan State University) found that diglycidyl ether of BPA (epoxy resin Epon82 8) can be polymerized with montmorillonite by intercalating agent CH3(CH2)n-NH3 + Rice grade polyether-clay composite. The structure of the intercalation agent is different, the distance between the layers can reach 18A, and then the self-polymerization of the epoxy resin of 75t becomes the continuation page. (When the invention page is not enough, please note and use the continuation page)

1270529 34.1A epoxy resin / clay material, and proved that its heat distortion temperature (heat, · distortion temperature) is improved, the regularity of the intercalating agent can be from monolayer to bilayer, even to Three-layer structure (pseudo_trimolecular), the interlayer distance is between 13.8~18·0 people. In this width intercalation layer, the epoxy resin can be polymerized, and the layered inorganic substance can be further divided to achieve the application effect of the nano material. Sakamoto Toyota developed an organic/inorganic nano-high-grade Lu sub-composite with the commercial success of [HsNlCHduCOCT Bu-Monte Dispersion in Nylon 6). It is described in Japanese Patent Publication No. 8-22946 that intercalation reaction is carried out with aminocarboxylic acid to enlarge the interlayer distance of the layered sulphate, and then caprolactam is intercalated between the interlayers. The condensation polymerization was carried out to form a layered niobate flake in a uniform dispersion structure in a polyamine (Nylon 6) resin. However, in addition to the polyamide resin, it is difficult to uniformly disperse the layered tantalate flakes in other resins. For example, it is very difficult to uniformly disperse the highly hydrophilic layered niobate in non-polar polyethylene or polypropylene. In order to solve this problem, Japanese Patent Publication No. 8-53 572 discloses that an intercalation reaction is carried out with an onion ion to enlarge the interlayer distance of the layered niobate and then mixed with the molten polyolefin resin. The layered tantalate flakes are formed into a uniformly dispersed structure in the resin. Although the organic gold ion can enlarge the interlayer distance of the layered tantalate, and the olefin resin is easily inserted continuously between the interlayers, the affinity of the organic intercalation agent to the olefin resin is still insufficient, and the layered niobate is required. Unlimited swelling is very difficult. ^Continued page (Notes on the use of the invention page, please note and use the continuation page) 1270529 Description of the invention Continuation of the article, Japanese Patent Publication No. 10-182892, the organic layered silicate and hydrogen-containing bond The functional olefin oligomer and the polyolefin resin are melted and kneaded, and the layered citrate can be infinitely swollen in the resin. This is because the affinity of the intercalating agent to the olefin polymer having a hydrogen bond-functional group (e.g., polyamine polymer) is strong. However, in order to uniformly disperse the layered niobate, a sufficient amount of oligomer must be present. However, the presence of a large amount of the oligomer in the resin lowers the mechanical properties of the resin, particularly the impact resistance. [Contents] The main object of the present invention is to provide a method for producing a nano-powder sheet, which can directly delaminate a layer of cerium-containing inorganic clay to form a nano crepe sheet. Another object of the present invention is to provide a method for producing a nanosheet which can be recycled and reused. In order to achieve the above object, the method for producing a nanosheet according to the present invention mainly comprises the following steps: (a) polymerizing a polyetheramine having a molecular weight of 1,000 to 100,000, p-cresol and formaldehyde to obtain Mannesamine (Amine Terminal- Mannich Oligomer; AMO) a polymer intercalation agent, wherein the formaldehyde is added at a rate of 0.01 to 20 ml per hour; (b) the mannisamine polymer intercalant is acidified with a mineral acid; (c) The acidified mannisamine polymer intercalant is mixed with water-swelled cerium-oxygen layered inorganic clay to carry out a cation exchange reaction, and directly demineralizes the cerium-oxygen layered inorganic clay; (d) in the step (c) In the resulting mixture, add an alkali metal or alkaline earth metal hydroxide or chloride aqueous solution and B β continuation page. (Note that the page is not sufficient for use, please note and use the continuation page) 1270529

Alcohol, and filtered; and (e) in the solid obtained in the step (6), adding a metal or alkaline earth metal hydroxide or chloride aqueous solution, ethanol, water and an organic solvent, and then standing still to obtain a nano Tablets in the lower aqueous solution. The polyetheramine of the present invention preferably has a molecular weight of from 1, 〇〇〇 to 1 〇, and is preferably from 1, 〇〇〇 to 5,000. The polyetheramine may be a polyoxypropylene diamine, a polyoxyethylene diamme, a poly(oxyethylene- oxypropylene) diamine adduct, or the like. Among them, polyoxypropylene diamine is preferred. The formaldehyde of the above step (a) is preferably added at a rate of 2 to 12 ml per hour; the molecular weight of the obtained mannisamine polymer intercalation agent is greater than 9,000, accounting for 25 to 100 wt%. The Mannis of the above step (6) The equivalent ratio of the amine polymer intercalation agent to the inorganic acid is 2 = 1 °. The inorganic acid may be hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid or the like. The cation exchange equivalent ratio of the Mannes amine polymer intercalant to the cerium oxide layered inorganic clay in the above step (c) is 2:1. The bismuth layered inorganic clay may be montmorillonite, kaolin, mica, talc (talc. The cation exchange equivalent of the chopped enamel inorganic clay is preferably 5〇~200 Meq/lOOg The hydroxide or chloride of the alkali metal or alkaline earth metal in the above step (d) is preferably sodium hydroxide. The amount of hydroxide or chloride of the alkali metal or soil test metal in the above step (d) It is preferably one-time equivalent. 0 Continued page (When the invention page is not enough, please note and use the continuation page) 1270529

Intercalation/ExfoHation Process

Reaction diagram A in the reaction diagram A, by polyoxyalkylene diamine (polyoxyalkylene diamine), para

Amine-terminatiog Mannich Oligomers (AMO) polymer intercalating agent obtained by polymerization of p-cresol and formic acid is acidified with hydrochloric acid to form an emulsion. The acidified Mannesamine polymer intercalating agent is mixed with the water-swelled cerium-oxygen layered inorganic clay to carry out a cation exchange reaction, and the mannisamine polymer intercalating agent can intercalate the layer of the cerium-oxygen layered inorganic clay. The distance is gradually enlarged and finally completely delaminated to obtain a ΑΜΟ/Clay mixture. Then, in the ΑΜΟ/Clay mixture, add the aqueous solution of sodium hydroxide to insert the AMO layer 0. (The invention page is not enough, please note and use the continuation page) 11

The 1270529 agent was replaced and filtered. The yield and purity of the nanosheets can be improved by repeating the displacement reaction, adding a large amount of ethanol and water, and extracting the AMO intercalant with toluene. After the reaction, the mixture is allowed to stand for stratification, and a Nano Silicate Plate is obtained in the lowermost aqueous solution, and the upper layer of toluene contains the Mannes amine polymer intercalant, which can be recycled and reused. In order to explain the present invention in more detail, the preferred embodiments are set forth below. The raw materials used in the examples of the present invention include sodium cation exchange type montmorillonite Kumpia F (Na+-MMT, CEC=115 meq/100 g); strutural units or first-order structures of primary montmorillonite (primary) Structure) is an average of 8-10 layers of lamellae, each layer thickness is 9.6-10A, and the layer-to-layer spacing is only about 12A. The secondary structure of montmorillonite is a hydrophilic silicate agglomerate of 0.1 to 10 μ size. 2, a pair (p-cresol, ACR0S company, Mw 108, m.p · 31 ~ 34 〇 C, b.p. 202 〇 C) °

And poly(propylene glycol bis (2-amino propyl ether)) (manufactured by Huntsman Chemical Co., trade name Jeff amine® D-2000, Mw 2000), structure The formula is as follows: [3 continuation page (When the invention page is not enough, please note and use the continuation page) 12 1270529

2 h2nchch2(och2ch) nh ch3 ch3 X= 33 (Approx. Mw=2000; Jeffamine® D-2000) °, formic acid (formaldehyde, made by ACROS, molecular weight Mw 30, 37 wt% aqueous solution) Window Example 1 In the examples, the montmorillonite should be pretreated first; the montmorillonite (10 g, 11.5 meq) is dispersed in hot water (1 L) at 80 °C, and stirred vigorously for 4 hours to make the montmorillonite swell to form a stable earth color. , evenly dispersed. Next, the following steps were carried out: (8) Synthesis of mannesamine polymer intercalant A formazan (13·6 g) and polypropylene glycol diamine (378.78 g) were dissolved in toluene and refluxed at 9 ° C for 3 hours. Next, formaldehyde was further added at a rate of 4 ml for 30 ml; and the temperature was raised from 90 ° C to 130 ° C. After 5 hours, the mixture was gelatinized and the formic acid reflux was stopped to give the product AMO (Amine-terminatiog Mannich Oligomers). AM 〇GPC analysis (Gel Permeation Chromatography) gave three peaks, Mw 3,142, 6,221 and 9,246; amine titration showed a primary amine of 0.4 μm / g, a secondary amine of 0.56 meq / g, no tertiary amine . Continued page (Please note and use the continuation page when the invention page is not available) 13 1270529

(b) Acidification of Mannesamine polymer intercalant. AM〇 (57.5g; 23meq) was dissolved in water and concentrated to 35 wt·% concentrated hydrochloric acid (1.2g; 11.5meq) at 80 °C. 30 minutes. (c) Delamination reaction The acidified AMO solution was poured into a swelled montmorillonite hot dispersion, and vigorously stirred at 80 ° C for 5 hours to score a layer of ΑΜΟ/Clay mixture. (d) First stage displacement reaction Add the AMO/Clay mixture of step (C) to one equivalent of Na〇H (4.6g). At this time, the AMO/Clay mixture will form a viscous liquid in a light yellow emulsified state. The viscous liquid is added to 750 ml of ethanol and filtered. The filtered solid is added to 1 L of ethanol and stirred evenly to obtain a light yellow translucent AM0/NSP mixture. Continued page (Insert description page is not enough, please note and use Continued) 1270529

The organic/inorganic ratio at this time is about 40/60. (e) Second stage displacement reaction The AMO/NSP mixture of the above step (6) was added to 1 L of ethanol and stirred well, and then 1 L of water was added thereto and stirred uniformly. Then, dip twice the equivalent of Na〇H (9.2 g) and mix well. After the final addition, add 1 L of toluene and mix well. After standing for one day, the solution is divided into three layers, and the uppermost layer is ruthenium dissolved in toluene, which can be recycled and reused. The middle layer is ethanol, and the lowermost aqueous solution is taken to obtain the main product nano-negral tablets. Comparative Example 1 Steps (8) to (e) of Example 1 were repeated; however, the cresol, polypropylene glycol diamine and formaldehyde of the step (a) were all reduced by half. Then, the distance between the montmorillonite layers in the step (c) was 61 A by XRD analysis, and direct delamination could not be achieved. The natural montmorillonite, the interlayer distance of Example 1 and Comparative Example 1, and the weight ratio of the organic component/clay are shown in Table 1. y Continued page (Note when the invention page is not enough, please note and use the continuation page) 1270529 Description of the invention Table 1 Natural montmorillonite Example 1 Comparative Example 1 Moerby "v: -Μ ; (AMO/Kunipia F ί ' 1 ι ;; 瞻 2:1:1 1:1:1 /HC1) ι : interlayer distance (A) 12 delamination 61 organic component / clay weight ratio a 0/100 83/17 73/27 organic Composition/Clay weight ratio b 0/100 83/17 72/28 aTGA Thermal analysis (850 ° C) 1 ten theory 値

Comparative Example 2 Steps (a) to (e) of Example 1 were repeated; however, the formaldehyde of the step (8) was added instantaneously. The obtained AMO has high fluidity and is analyzed by GPC to obtain three peaks, Mw 2,034, 4,334 and 6,690 respectively. The product of step (c) was only intercalated by XRD analysis, and there was no delamination. The product of step (d) is pale yellow; in the product of step (e), both clay and AMO are present in the toluene layer. The reason for the analysis is that the molecular weight of the AMO in the step (8) is low, and the interlayer distance of the clay cannot be effectively expanded to achieve the direct delamination effect. 16 1270529

Comparative Example 3 Steps (a) to (e) of Example 1 were repeated; however, if the step (d) was not added with ethanol, the mixed solution could not be excessively entangled. Process amplification test r

I Steps (a) through (6) of Example 1 were repeated; however, each material was increased to a 10-fold dose. Finally, the same nanopellet can be obtained in step (e). As can be seen from the above examples, the present invention can control the spacing of the clay layers to the delamination state by controlling the molecular weight of the AMO intercalating agent, the appropriate proportion of the amine groups or the degree of acidification, especially one-step direct delamination. The prepared nanosheets have a monolithic primary structure (NSP). The clay modified by the present invention is oleophilic in compatibility with the polymer due to the modification of the AMO intercalating agent. In addition, since the quaternary amine salt after acidification in the structure of the AMO intercalation agent can be used as a cationic initiator, the ruthenium/Clay can be cross-linked with the epoxy resin, thereby dispersing the silicate layer structure of the clay, and Dana The dispersion of the meter scale. The nanosheet of the present invention can be blended with an organic polymer to improve the mechanical properties such as solvent resistance, heat resistance, gas barrier properties, rigidity, tensile strength and back-returnability of the molecule. 17

Claims (1)

1270529 Patent Application No. 1. A method for producing a nano tablet, comprising the following steps: (8) Polymerizing a polyetheramine having a molecular weight of 1,000 to 100,000, a methyl hydrazine and a waking to obtain a Mannes amine (Amine Terminal-Mannich) Oligomer; AMC® polymer inserting agent, wherein the formic acid is added at a rate of 0.Q1 to 20 ml per Xiaoling; (b) acidifying the mannisamine polymer intercalating agent with a mineral acid; The acidified mannisamine polymer intercalation agent is mixed with the water-swelled cerium-oxygen layered inorganic clay to carry out a cation exchange reaction with an exchange equivalent ratio of 2:1 and a layered inorganic clay Direct delamination; (d) in the mixture obtained in the step (c), adding an alkali metal or alkaline earth metal hydroxide or chloride aqueous solution and ethanol, and filtering; and (e) in the solid obtained in the step (6) After adding an alkali metal or alkaline earth metal hydroxide or an aqueous chloride solution, ethanol, water and an organic solvent, the mixture is allowed to stand for stratification, and the nano sized tablet is obtained in the lower aqueous solution. 2. The method according to claim 1 Which step The molecular weight of the polyetheramine of (8) is from 1,000 to 10,000. 3. The method of claim 1, wherein the polyetheramine of the step (a) has a molecular weight of 1, 〇〇〇 to 5,000. 4 The manufacturing method according to claim 1, wherein the polyetheramine of the step (8) is selected from the group consisting of polyoxypropylene diamine, polyoxyethylene diamine, and poly(ethyl). Ether-propyl ether) Diamine poly (oxyethylene- [Continuous to the next page (Please note and use the continuation page when the patent application page is not available) 1270529 Patent application continuation page oxypropylene) diamine adduct 0 5. If applying for a patent The method of claim 1, wherein the polyetheramine of the step (a) is a polypropyl ether bisamine (P〇1y〇xyPr〇Pylene diamine). 6. The method of claim 1 , wherein the formaldehyde of the step (a) is added at a rate of 2 to 12 ml per hour. 7. The method of claim 1, wherein the mannisamine polymer intercalant of the step (a) The molecular weight of more than 9,000 accounts for 25~100 wt% 〇8. The method of claim 1, wherein the equivalent ratio of the Mannes amine polymer intercalant to the inorganic acid in the step (b) is 2: 1. 9. As described in claim 1 The method, wherein the inorganic acid of the step (b) is selected from the group consisting of hydrochloric acid, sulfuric acid, phosphoric acid, and nitric acid. 10. The method of claim 1, wherein the step (c) is a layered inorganic clay system It is selected from the group consisting of montmorillonite, kaolin, mica and talc. 11. The manufacturing method according to claim 1, wherein the cation exchange equivalent of the bismuth layered inorganic clay of the step (c) is 50 〜2〇〇meq/100g 〇1270529 □ continued page ( When the patent application scope page is insufficient, please note and use the continuation page.) The method of claim 1 is as follows. For the method described in claim 1, the alkali metal or alkaline earth of the step (d) Metal hydroxide or chloride sodium hydroxide. 13. The method of claim 1, wherein the step (d) is to add one equivalent of an alkali metal or alkaline earth metal hydroxide or chloride. The method of claim 1, wherein the organic solvent is selected from the group consisting of ethers, ketones, esters, nitriles, saturated hydrocarbons, chlorinated saturated hydrocarbons, and aromatic hydrocarbons. class. The method of claim 1, wherein the organic solvent is selected from the group consisting of tetrahydrofuran, diisopropyl ether, methyl tert-butyl ether, methyl isobutyl ketone, acetonitrile, Ethyl acetate, pentylene, hexane, heptane, cyclohexane, dichloromethane, benzene, toluene, xylene, chlorobenzene and methoxybenzene. 16. The method of claim 1, wherein the step (e) comprises adding one to three equivalents of an alkali metal or alkaline earth metal hydroxide or chloride. 17. The method of claim 1, wherein the step (e) of the organic solvent layer comprises a Mannesian interbody molecular intercalant' recyclable. 18. A nanosheet which is obtained by the method of claim 1 and wherein the nanosheet obtained in the step (e).