TW593480B - Copolymer direct exfoliation and nano silicon flake derived therefrom and method for producing the same - Google Patents

Abstract

The present invention provides a copolymer directly exfoliated clay having an excellent surfactant performance and capable of being used as a polymer reinforcing agent and a nano silicon flake. A bipolar intercalating agent is produced by polymerizing a polyoxyalkylene amine having a molecular weight of over 1800 with a polypropylene-grafted-maleic anhydride (PP-g-MA). The intercalating agent and a siloxy layered inorganic clay performs an emulsification intercalating reaction in water so the clay is completely exfoliated to obtain a copolymer directly exfoliated clay. Its method of production comprises obtaining a bipolar intercalating agent by polymerizing a polyoxyalkylene amine having a molecular weight of over 1800 with a polypropylene-grafted-maleic anhydride (PP-g-MA); forming an emulsion from the intercalating agent by using an inorganic acid to perform an acidifying reaction in an organic solvent; and adding a water-swollen siloxy layered inorganic clay into the emulsion to receive a vigorous mixing in a reaction system at 60 to 180 DEG C and normal pressure to 500 psig for undergoing an emulsion intercalating reaction in water to obtain a fully exfoliated copolymer directly exfoliated clay. Optionally, the clay thus obtained receives a further extraction by a hydroxide or chloride of an alkaline metal or an alkaline earth metal for obtaining a nano silicon flake, while recycling the intercalating agent.

Description

593480 V. Description of the invention (1) Field of the invention] The present invention relates to

Copolymer macromolecule directly delaminated clay and A sheet, and its manufacturing method, especially by using polyoxyalkylene amine with a molecular weight of 18,000 or more and grafting with polypropylene (PP-g-MA) Amphoteric intercalating agent obtained by polymerization, and emulsifying intercalation reaction with siliceous layered inorganic clay in water with stomach agent. The copolymerized polymer obtained by completely delayering 1 # layer of soil directly delaminates the clay. g. To make the mold to extract with alkali metal or alkaline earth metal hydroxide or chloride, one meter stone tablet and its manufacturing method. Pieces [Description of Known Skills], Shi Xi oxygen layered inorganic clay was often used as a catalyst and polymer reinforcement material, which can loosen the clay through the intercalation reaction material of organic quaternary ammonium salt i ^^ ralating) Sandwich, the distance between the layers at this time is about. This loose inflammatory layer can allow monomers to enter and exit, and then organic / inorganic nanometer high through polymerized decompression and delamination (eXf〇Hate); the material can be used as a reinforcing material for polymer materials. Improve the high score, mechanical properties, mechanical properties, gas barrier properties, and flame resistance. Organic / material-free materials are considered important materials in the new century. This kind of question is used as a very important lesson in research and development in academia and industry. For example, τ years' literature in this area And many patents have been published. Examples include bisphenol A ^ PlnnaVaia (Michigan State University), a diglycidy 1 ether of BpA,

593480 5. Description of the invention (2) The oxygen resin Epon82 8) can be polymerized into nano-scale polyether-clay composites by intercalating agent ((: ¾) n-NH / and montmorillonite. The intercalation agent's structure < + Same, the interlayer distance can reach 1 8 Α, and then it is polymerized by 75 ° C epoxy resin to become 3 4. 1 i epoxy resin / clay material, and its heat distortion temperature is proved (heat distortion temperature) Ascension, the regularity of the poplar agent can be from a monolayer to a bilayer, or even a two-layer structure (pseudo-trimolecular), with an interlayer distance of 13. gqg 〇 又 之间. In this width Intercalation, one by one milk resin --- ^, sub-foot further disperse the layered inorganic material to achieve the application effect of nanomaterials. And Japan's Toyota Corporation developed a dispersion of rf (CH2) 11C00 '] -montmorillonite Nylon 6 is the first commercially successful organic / inorganic nano polymer composite material. It is described in Japanese Announcement No. 8-2 2 9 4 6 and an intercalation reaction with aminocarboxylic acid is performed to separate the layers. Interlayer ^ giant = enlarged 'then caprolactam monomer (caprolactam) in the interlayer Condensation polymerization is carried out between layers to make the layered silicate flakes uniformly dispersed in the polyamide (N y 1⑽ 6) resin. However, except for the polyamide resin, the layered silicate flakes must It is very difficult to uniformly disperse in the resin. It is very difficult to uniformly disperse the layered stone syrup S with high hydrophilicity in non-polar polyethylene or polypropylene. Organically solve the problem of this problem, Japanese Public License 8 It is recorded in No. 5 3 5 72 that the interlayer reaction is carried out with the onium mate, and the layered silicic acid is thinned and then mixed with the molten polyolefin resin. The layered silicon layer can form a uniformly dispersed structure in the layer t. Although the interlayer distance of the organic layered oxalate is enlarged, the olefin resin is easier to

Page 6 593480

τ j continuous shell insertion, but because of the affinity of the organic intercalating agent and the olefin resin, it is very difficult to make the layered silicate infinitely swell. However, it is described in No. 1 8 2 8 9 2 that the organic layered fossilate is melt-kneaded with an olefin oligomer and a polyolefin resin containing a ^ g: group, and a bond disilicate Unlimited swelling in resin. This is due to the affinity of the intercalating agent with the hydrogen-containing hydrazine (i.e. polyamine polymers); However, in order to uniformly disperse the layered silicate, the original copolymer must be used. However, a large amount of oligomers in the resin will reduce the tree's resistance, especially the impact resistance. θ < Mechanical properties [Summary of the invention] The present invention discards the old intercalation method, and uses the special interfacial properties of the amphoteric agent to perform emulsification and delamination (emulsi〇n layer exf 〇1 iat ion). Clay direct exfoliation 'Nano-silicon wafers to obtain new organic / inorganic surfactant layers. Therefore, in the present invention, the amphoteric intercalating agent obtained by polymerizing polyoxyalkylene amine with a molecular weight of 1800 or more and polypropylene grafted with maleic anhydride-, amine (PP g-Μ A), _ amine The radical is acidified to form a quaternary ammonium salt with a cation and / or a special interfacial property of the terminal agent, and then intercalates with the sodium ion in the clay layer. It enters the clay interlayer in an emulsified manner, and cationic soil is directly delaminated in one step to obtain a new type of organic / oxygen ^ layer inorganic clay. Because this stable compound has both polar, organic polymer complex and non-polar lipophilic organic carbon chain structure, the inorganic layered structure of i water exhibits a special oil-water interface.

593480 5. Description of the invention (4) The special interface phenomenon can reduce the interface tension of toluene / water to about 3.8 dyne / cm at a concentration of 100 ppm. This new type of surfactant has a low critical micelle concentration (CMC) and can form hard structural micelles. This special interface phenomenon facilitates the uniform dispersion of organic / inorganic hybrid materials in polymers, in order to modify polymers to give them inorganic properties. Therefore, the copolymerized polymer direct delaminated clay of the present invention is a new type of inorganic / organic surfactant, which can be used as an emulsifier, a dispersant, and the like. In addition, the directly delaminated clay of the copolymerized polymer of the present invention can also be used as a polymer reinforcing agent, and blending with the polymer can improve the mechanical properties of the polymer such as heat resistance, gas barrier properties, rigidity, tensile resistance, and reverse reversibility. . In addition, because the amphoteric intercalating agent has the same structure as polypropylene, the copolymerized polymer of the present invention can be directly delaminated with clay and blended with polypropylene, which can change the polarity of polypropylene and improve its resistance to organic dyes and inks. ) And other adhesion properties, making polypropylene more versatile. The present invention uses a method of fine emulsification and simultaneous intercalation / delamination to delaminate clay with primary and secondary structures to obtain a basic unit of clay flakes. The basic unit of clay flakes has a high aspect ratio and is a flake-shaped nanomaterial, unlike the conventional spherical, layered, and columnar nanomaterials. The delaminated clay of the copolymeric surface molecules prepared by the present invention can be further extracted to obtain a completely delaminated nano silicon wafer. Conventional intercalating agents, including 12-aminolauric acid, hexadecylamine, fatty amine, and bis (2-hydroxyethyl) fluorenyl tallow alkyl Bis (2-hydroxyethy 1) methy 1 tallow alkyl ammonium

593480

5. Description of the invention (5) Amines or ammonium salts such as chloride) and stearylamine. The polar group of this type of low molecular intercalating agent can be combined with charged inorganic layered molecules to form a polar valence bond, and change the hydrophilicity of clay into an organic solvent-friendly property. In other words, that is to increase the affinity of the clay to the organic early body or the plutonium molecule, so as to facilitate the next delamination reaction. However, through intensive research, the present inventors have found that a polymerization reaction using polyoxyalkylene amine having a molecular weight of 18,000 or more and polypropylene-graft maleic anhydride (PP-g-MA) can obtain an amphoteric intercalating agent. , Using its terminal amine group to acidify to form a quaternary ammonium salt with cations, and then carry out a cation exchange reaction with the sodium ion of the interlayer of soil to directly delaminate the clay, @ to obtain a polymer organic / inorganic composite The compound has excellent surfactant effectiveness. Therefore, in the present invention, the amphoteric intercalating agent obtained by using a polyetheralkylene amine having a molecular weight of 18,000 or more and a polypropylene grafted maleic anhydride (PP-g-MA) to perform a polymerization reaction is used to modify the stone. Evening layered inorganic clay. The polyetheramine used in the present invention may be selected from the group consisting of polyoxypropylene diamine, polyethylethylene diamine, and poly (ethylether-propyl) diamine (poly (oxyethylene-oxypropylene) ) diamine) 〇 These substances are commercial products such as Jeffamine D2000 [poly (propylene glycol) bis (2-amino propyl ether), Mw 2000], Jeffamine D4000 [polypropylene glycol Poly (propylene glycol) bis (2-amino propyl ether), Mw 4000] AJeffamine

Page 9 593480 V. Description of the invention (6) ED2001 [(polypropylene glycol block-polyethylene glycol block-polypropylene glycol block) double

(2-aminopropyl ether) (poly (propylene glycol) -block-poly (ethylene glycol) -block-poly (propylene glycol) bis (2-aminopropyl ether)), Mw 2000], etc., among which Jeffamine ED2001 is The best; others are such as T3000 [tri-functional po 1 y (propy 1 ene g 1 yco 1) 2-amino propyl ether), Mw 3000], T5000 [trifunctional poly 1 Propylene glycol 2-aminopropyl ether (tri-functional polyCpropylene glycol) 2-aminopropyl ether), Mw 5000] and the like. (The structural formula of the Jeffamine series is shown below) H2NC H CH 2 〇CH 2CH χΝΗ 2 CH 3 CH 3 X = 3 3 (Approx. Mw = 2 0 0 0; JeffamineR D-2000) X = 68 (Approx. Mw = 4 0 0 0; JeffamineR D-4 0 0 0)

nh2 z h2nchch2 ochch2 (och2ch2) (OC ch3 ch3

Average ^ x + z = 5, y = 3 9. 5 (Approx. Mw = 2 0 0 0; JeffamineR ED-2001)

Page 10 593480 V. Description of the invention (Ό Inorganic / organic nanocomposites are materials with two different phases, and at least one phase has a nanoscale regime dispersion. Under uniform dispersion, that is, at high contact area (Surface to volume ratio) state, increase mechanical properties. Due to compatibility (1 arae 1 exists' structure (P quaternary ammonium chain between the micro-molecular distance). Interstitial crystals often need to go through. Mongolian clay (this, good. Generally 1 ae), and the affinity between the layer and the primary fine coagulation is in the ionic salt, the non-conjugated layer is dispersed, and the non-intercalated composite structure is determined by the organic and inorganic matter. The montmorillonite structure of the phase has an average 10-layer parallel layered layer with a layer diameter of about 10 nm (i ·, ·, ΙΟοΑ). The distance between the layers is only about 1 21, which is the smallest first-level structure.) Hydrophilic silicate (siHcate) aggregates into a secondary structure and has a low organic power. Improving the compatibility between the two requires the ability of the clay layer to exchange with the organic quaternary ammonium salt. Intercalation Increasing the layer distance 'usually reaches about 20, and using ionic valence' as the intercalation to modify the clay makes it an organic (intercalation) system layer and the layer exists at a fixed distance. Exfoliati. n) The distance and direction of the shape from the rule exists. This is the delamination process ..., and the host clay and macromolecules pass through a further process to exfoliate the soil (montmor i 1 loni te, MMT) to Hirsch + ^ a】 · ..., ,, Zhu Rishi Shiming Ming (ilumino-silicate clay), structural formula and ancient — another layer of tetrahedron

593480 5. Description of the invention (8) silicon dioxide (tetrahedral silicate) and sandwich octahedral alumina (octahedral alumina). Observation by electron microscope is 0 · 1 ～ 1〇 # aggregation of small and large, and the structural units (struturai units) are 16 planes (8 planes) or 8 layers (iameliae), each layer thickness is 9.6-10 A. Therefore, the primary particle has a height of 80-1 00 A and a radius of 300 A. The siliceous layered inorganic clay used in the present invention is selected from the group consisting of montmorillonite, kaolin, mica, and talc, among which is modified commercial montmorillonite. Soils are better, such as aliphatic ammonium intercalated clay (closite 20A) and sodium cation exchange type montmorillonite MMT (Kunipia F). In addition, the% ion exchange equivalent (cation eXChange capacity of clay (CEC)) of the siliceous layered inorganic clay used in the present invention is preferably 50-200 meq / 1OOg. When the cation parent exchange equivalent is less than 50meq / ioog, the organicization achieved through ion exchange is insufficient, and the swelling of the clay is not easy; when the cation exchange equivalent is higher than 200 meQ / 10 gram, interlayer bonding is achieved. Too much force can also make clay swelling very difficult. The manufacturing method of the direct delaminated clay of the copolymer polymer according to the present invention is obtained by polymerizing a polypropylene grafted maleic acid if (Pp-g_MA) by a knife with an amount of more than 1800 (p0yyxy aikylene amine). The amphoteric intercalating agent L is acidified with an inorganic acid in an organic solvent to form an emulsion, and then mixed with water-swelled Shixian layered inorganic clay, at a temperature of 60 to 8000 and atmospheric pressure to 50 ps. The 1 g reaction system was vigorously stirred to perform an emulsification intercalation reaction in water to obtain a completely delaminated copolymerized polymer and directly delaminated clay. this

Page 12 593480 V. Description of the invention (9) The important discovery in the invention is that polyetheramines with molecular weights lower than 8000 are not able to achieve the effect of high interlayer intercalation, let alone direct delamination. The aforementioned acidification reaction type amphoteric intercalating agent is performed in an organic solvent to form an emulsion, the organic solvent is selected from the group consisting of ethers, ketones, esters, moon | types, saturated hydrocarbons, gasified saturated hydrocarbons and aromatics. Hydrocarbons and so on. Specifically, it can be tetrahydropyrene. Pyran, diisopropyl ether, methyl tert-butyl ether, fluorenyl isobutyl ketone, ethyl salt, ethyl acetate, amyl alcohol, hexane, heptane, cyclo Hexane, dichloromethane, benzene, toluene, xylene, chlorobenzene and methoxybenzene. Among them, xylene or xylene is preferred.

In addition, if the intercalating agent is not subjected to an acidification treatment, most of the intercalating agent will not be able to enter the interlayer of the clay during the emulsification intercalation reaction, resulting in poor emulsification and intercalation effects. Useful acidifying agents are inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid and nitric acid. The higher the temperature of the acidification reaction, the smaller the diameter of the amphoteric intercalating agent, and the smaller the diameter of the amphoteric intercalating agent, the easier it is to achieve the delamination reaction. The aforementioned acidification temperature ranges from 80 to 100 ° C. Preferably, the diameter of the amphoteric intercalating agent obtained after acidification is less than 200 nm. The directly delaminated clay of the copolymerized polymer prepared by the present invention can be further extracted with hydroxide or gaseous substance of metal or alkaline earth metal to obtain a nano-stone tablet. The method is to dissolve the prepared polymer directly delaminated clay into an organic solvent at room temperature to 110 ° C to form a slurry a; and then disperse the siliceous layered inorganic clay in hot water and stir vigorously. Forms B; then mixes A and B, and stirs vigorously at 60 to 80 ° C for 10 to 60 minutes, and then adds alkali metal or alkaline earth metal hydroxide or chlorine at a concentration of 1 to 5N Aqueous compound solution 3 0 to 6 0 0 m 1 Stir vigorously at 60 to 80 ° C for 2 to 4 hours, then stand still

Page 13 593480 5. Description of the invention (ίο) After layering, the upper layer liquid is organic and can be recycled and reused, and the lower layer liquid is inorganic, that is, nano silicon wafers dispersed in water. The above-mentioned rat oxide or gaseous alkali metal or alkaline earth metal is preferably emulsified by wind. The organic solvent used to form the slurry A in the aforementioned extraction step is the same as the organic solvent used in the acidification step, and will not be described again. Due to the hydrophobic nature of the polypropylene bond, it is not compatible with the highly polar sodium cation-exchange montmorillonite (MMT). Therefore, in the present invention, 5 ^ propylene with maleic anhydride (MA) functional group is grafted onto maleic acid Xin (pp — g — ΜΑ) 'utilizing the high reactivity of maleic acid and amine group, and A molar ratio of 1: 1 with an anhydride / amine group is reacted 'to graft a diamine containing a polyether chain (such as the polyetheramine of the present invention) onto PP-g-MA to form a comb ( com-iike) type amphoteric polymer. The comb-shaped polymer main chain is a non-polar polypropylene main chain, and the comb-shaped side chain is provided with a polar polyalkyl ether [such as polyoxyethylene (POE) or polypropyl ether (polyoxypropylene). , POP)] and terminal amine groups. By acidifying the terminal amine groups of this comb-shaped polymer to make it a positive valence, it becomes a quaternary ammonium salt, which undergoes a cation exchange reaction with the interlayer sodium cations of Νί-MMT, and introduces the polymer into the clay layer to perform the emulsion intercalation reaction. This method of emulsifying into the clay interlayer to delaminate the siliceous inorganic clay has never been seen in the literature and commercial manufacturing methods. It is a novel and progressive invention. The reaction between the aforementioned polypropylene grafted maleic anhydride (PP_g-MA) and polyetheramine is because maleic anhydride has a high ring tension and easily reacts with nucleophilic molecules, so the Γ-aliphatic amine is at 7 ( fc

593480 5. Description of the invention (11) --- Ring-opening reaction with maleic anhydride 'becomes a structure with carboxylic acid (C00H) and amide functional groups, and the reaction is shown in the figure below

+ NH2 (j: HCH2-- | 〇Cj: HCH2 ^ 〇CH2CH2-)-(〇CH2 ^^-^ CH3 CH3 CH3

OH NH < pHCH2 ^ 〇 (pHCH2 ^ 〇CH2CH2)-(〇CH2 ^ H) -NH2 CH3 CH3 C CH3

丨 In addition, from the FTIR spectrum of PP-g-MA in Figure 1, it can be seen that 2800 ~ 3000 cm is the absorption peak of ^ 3, and 15 0 0 and 1 430 cm- 丨 respectively represent the absorption peaks of Cit and it. The most important thing is that the symmetrical and asymmetric absorption peaks of c = 〇 on the maleic anhydride ring are 1852 respectively.

With 1J79 cm-l. From Figure 2 pp-g — FTIR spectrum after ring opening reaction with D2 0 0 0 and Figure 3 PP-g — FTIR spectrum after ring opening reaction with ED 2 00i, it can be seen that due to the opening of maleic anhydride Ring results in 1 85 2 and 1 7 7 9 cnH double absorption

Page 15 593480 V. Explanation of the invention (12) The peak disappears, and the polyether segment 1 1 0 4 cm "(C-0-C stretching) and 1704 cm- 丨 (imide) (carbonyl)). Therefore, the progress of the reaction and the extent of the reaction can be clearly identified by FTIR. The aforementioned invention uses the terminal amine group of the synthesized comb-type polymer side chain to undergo cation exchange reaction with clay after acidification, and introduces the polymer into the clay layer for emulsion intercalation reaction. The non-polar polypropylene main The chain is introduced into the clay layer through the comb-shaped side chain to increase the probability of the main chain intercalation entering the clay corridor. The response is as follows:

Page 16 593480 V. Description of the invention (13)

Intercalation clay interlayer distance = 19 A particle size approximately l " m in toluene (laser particle analysis) (laser particle analysis)

Because the surface of natural clay is hydrophilic, it can be uniformly dispersed in water, but it is incompatible with most polymers. Therefore, it will form phase separation during melt-kneading and cannot achieve micro-fine dispersion. Improved clay by

Page 17 593480 V. Description of the invention (14) It is introduced into organic molecules, and it is partially non-polar, compatible with polymers, so it can be blended with polymers to modify polymers. Modified polymers such as epoxy resin, polypropylene (PP), polyethylene terephthalate (PET), polyethylene (ps), and epoxy Gauge polystyrene (SPS), polyurethane (PU), Nylon, and styrene-propylene moon copolymer (SAN). [Detailed description of the preferred embodiment] In order to explain the present invention in more detail, the preferred embodiments are listed below. When the scope of implementation of the present invention cannot be limited by this, that is, what is generally made according to the scope of the patent application and the description of the invention Simple equivalent changes and modifications should still fall within the scope of the patent of the present invention. Materials used: 1. Cation exchange equivalent CEC = 115 meq / 100 g of nano cation exchange type montmorillonite Kunipia F (Na + -MMT). 2. Polyacrylamide grafted maleic anhydride (pp-g-MA, manufactured by Eastman, trade name: Epolene E-43 or MPP-9100, no further purification required). Gel permeation chromatography weight average molecular weight Mw 9100, number average molecular weight Mη 3900, and titrated acid value 47 rag KOH / g. The maleic anhydride content is 4% by weight, or there are 3.7 maleic anhydride units per polymer chain. The structural formula is shown below

Page 18 593480 V. Description of the invention (15)

3. (polypropylene glycol block-polyethylene glycol block-polypropylene glycol block) bis (2-aminopropyl ether) [poly (propylene glycol) -block-Poly (ethylene glycol) -block-poly ( propylene glycol) bis (2-aminopropy 1 ether)] (manufactured by Huntsman Chemical Co., brand name Jeffamine ED2001, Mw 2000).

According to the following steps, an amphoteric intercalating agent obtained through the polymerization reaction of polyetheramine and polypropylene grafting is prepared, and an intercalating agent using the intercalating agent ^ A anhydride layered inorganic clay is obtained to obtain an intercalating agent. Delaminate the clay directly with Shixi Polymer in complete water. Total I 1 of the layer. Swelling step of Shixi oxygen layered inorganic clay: Take 5 g of Kunipia F (Na 10-MMT) and disperse it in hot water, stir vigorously for 4 hours, so that the aqueous solution forms a soil 807 dispersion. . Stability% $

Page 19593480 V. Description of the invention (16) 2 · Synthesis steps of amphoteric intercalating agent: Put 37 g of PP ^ g-ΜΑ (containing 15 mmol of maleic anhydride) in toluene and 'heat to 120 ° C'. Add 30 g (15 mmol) of ED 2 01, and the mixture forms a gel-like precipitate in a toluene solution. This is an amphoteric intercalator (PPtMA / ED2 0 0 1). Acidification treatment steps:

Dissolve 13.2 g of amphoteric intercalating agent (pp —g —MA / ED2000, containing 5 75 meci terminal amine group) in toluene, add equal molar number of hydrochloric acid (HC1), and mix at 80 ° Acidified for 30 minutes at C to form an emulsion. 4. Emulsification intercalation reaction step: Pour the acidified emulsion into the dispersion of step 1 and stir vigorously for 5 hours under a reaction system of 80 14.7 psig for cation exchange reaction. The reaction solution was left to stand to separate the layers. After filtration, it was dried in a vacuum oven at 80 t for 24 hours to obtain a light-colored solid compound (PP-g-MA / ED2 0 0 1 / MMT). The obtained composite was analyzed by X-ray diffraction, and the distance between layers was measured. Reproducible components of inorganic / organic reaction products were identified by TGA thermal analysis. 5. Preparation method of nano silicon wafer: 2 g of the composite (pp-g-MA / ED2 01 / MMT) prepared above was dissolved in 100 ml of toluene at 110 ° C to form a slurry a. Take 5 g Na +-MMT dispersion

Page 20 593480 V. Description of the invention (17)

; In hot water of I ^^, stir vigorously to form slurry B. Syrup A 222π2 was vigorously mixed at 80 ° C for 30 minutes. Then, add ϋtami & aqueous solution ml and stir vigorously at 80 ° C for 3 hours. The second layer of liquid is organic (pp-g_MA / ED2000) can be recovered, and the next 4 liquids are inorganic. , That is, nano silicon wafers dispersed in water. [Analysis of experimental results 1. Interfacial properties Because the main bond polypropylene is lipophilic, and the clay silicate layer, interlayer hydrated sodium ions, and polyether segments are hydrophilic, the organic intercalated inorganic material prepared by the foregoing method has Special interface properties. Figure 4 shows the interfacial tension diagram of the amphoteric polymer intercalation agent and its interface with Na + j-MMT after delamination and delamination. PP-g-MA / ED2 0 0 1 / N4 -MMT intercalation, delamination, and PP-g_MA / D2000 / N4 -MMT intercalation and delamination all have similar critical micelle concentration (CMC) ). The intercalated silicate layer still retains the layered arrangement. The polyether segment entering the silicate layer cannot fully exhibit its properties. Therefore, the interfacial behavior of the PPgMA / D2000 / MMT intercalation and PPgMA / ED2001 / MMT intercalation No significant difference. The delaminated silicate layer is no longer layered. The polypropylene main chain and polyether segment can be completely exposed outside the silicate layer, so the polyether chain fully exhibits its properties. The lipophilicity of D2 0 0 0 and the hydrophilicity of ED 2 0 0 1 make the interface behavior significantly different. At 1 wt% of PPgMA / ED2 0 0 1 / MMT delamination, the interface between toluene and water is almost non-existent.

Page 21 593480 V. Description of the invention (18) 2 · T G A analysis The polymer intercalating agent in the intercalated silicate cannot fully enter the clay oxalate layer. The pyrolysis temperature of the polymer intercalating agent in the intercalated oxalate is greatly affected by clay. The polymer intercalating agent in the dehydrated oxalate is dispersed on the surface of the oxalate in the clay. The cracking temperature of the polymer intercalating agent in the delaminated silicate is less affected by the clay. The results are shown in Figure 5. 3 · Solvent dispersibility analysis The surface of natural clay is hydrophilic, so it can be evenly dispersed in water.

Most organic solvents are incompatible. The modified clay is partially non-polar due to the introduction of organic molecules, and is compatible with organic solvents. After the modified clay was subjected to ultrasonic vibration, the dispersion stability was observed. The results are shown in the table below. 4 · Particle size analysis ^ From the results in Table 2, PPgMA / ED20 01 can be acidified at high temperature, regardless of the conditions of H intercalation (0 / W) or reverse (w / 〇) in the aqueous phase. L TE In the case of D 〇1, the obtained particle size is smaller than that of low-temperature acidification, and the acidification? The higher the particle size, the smaller 'shows that PPgMA / ED2 0 0 1 has a ceremonial effect under high temperature environment. Therefore, if PPgMA / ED 2 0 0 1 is acidified at high temperature, it is easier to delaminate when performing ion exchange at local temperature. According to the description of the bucket + ft, a copolymerized polymer of the present invention can be directly delaminated and its diffractive stone tablets and a manufacturing method thereof, which can obtain a completely delaminated copolymerization.

Page 22 593480 V. Description of the invention (19) The polymer can directly delaminate clay and can be further extracted with alkali metal or alkaline earth metal hydroxide or chloride to obtain a nano silicon wafer. Recycling and reuse are in full compliance with the provisions of the Invention Patent Law. It is a highly technical creation that uses the laws of nature. Therefore, you have filed an application for an invention patent in accordance with the law.

Page 23 593480 V. Description of the invention (21) Table 2 PP-g-MA-ED 2 0 0 1 Particle size analysis Sample acidification temperature (° c) Measurement temperature (° c) Effective particle size Effective Diam. (Mil) Average Mean Diam. (Nm). Size Distribution (nm) Remark PPgMA / ED2001 W / 0 85 25 353.8 255.9 192.7-325.7 Milky white solution 74 371.7 120,4 65.9-131.8 Transparent clear liquid, white precipitate PPgMA / ED2001 O / W 85 25 146.1 72.1 53.4-159 Milky white color 74 361.1 40.6 38.5 Milky white color PPgMA / ED2001 W / O 25 25 2711.4 2003.7 1968.8-2029.9 Milky white color, ¾ Cotton floc 74 150.9 101 83.4-115.9 Milky white solution Color, cotton fleece PPgMA / ED2001 O / W 25 25 1578.9 1184.7 1177.7-1198.9 milky solution color 74 680.2 465.8 436.2-477.8 milky solution color

IBH 593480 Brief description of the diagrams Schematic diagrams Fig. 1 Fig. 2 Tgl — · Garden 2 Fig. 4 FTIR spectrum of pp-g-MA FTIR spectrum of PP-g-MA / D20 0 0. FTIR spectrum of PP-g-MA / ED20 0 1. Amphoteric polymer intercalating agent and its interfacial tension in toluene / water after intercalation and delamination with Na + -MMT. Figure 5: (A), showing pp-g-MA-D2000 / MMT intercalation temperature and pressure; (B), showing PP-g-MA-D2000 / MMT Intercalated MMT TGA curve comparison (C), showing PP-g —JjA-D20 00 / MMT curve and differential curve; (D), showing PP ~ g-MA-ED2001 / 1 / MTT layer temperature and pressure; (E), showing PP ~ g-MA-ED2〇〇1 / MMT curve and differential curve.

Exfoliated MMT, different E X f ο 1 i a t e d Μ Μ T and

Exfoliated MMT TGA

Exf◦1iated MMT

Exfoliated MMT TGA Figure 6 Table 1 Table 2 is a schematic diagram of the manufacturing method of the present invention. The particle size analysis of the solvent-dispersed PPHA-ED20 01 modified with different intercalating agents for Na + -MMT.

Page 26

Claims (1)

593480 6. Application for special thorn Suwei 1. A copolymerized polymer directly delaminated clay, which is grafted with polyoxyalkylene amine and polypropylene maleic anhydride (PP-g-Μ) with a molecular weight of 1 800-20,000. A) An amphoteric intercalating agent obtained by performing a polymerization reaction, and using the intercalating agent to perform an emulsification intercalation reaction with silica-layered inorganic clay in water to obtain a fully delaminated copolymeric polymer directly delaminated clay. 2 · The copolymerized polymer directly delaminated clay according to item 1 of the scope of the patent application, wherein the ratio of the Moire number of the amphoteric intercalator to the cation exchange equivalent of Shixi oxygen layered inorganic clay is 1. 3 ~ twenty one. 3. The copolymerized polymer directly delaminated clay according to item 1 of the scope of the patent application, wherein the polyetheramine is selected from the group consisting of polyoxypropylene diamine and polyethyl ethylene diamine And poly (oxyethylene ~ oxypropylene) diamine adduct ° 4 · The copolymerized polymer described in item 1 of the patent application directly delaminates the clay, wherein the silicon oxide layer The inorganic clay-like system is selected from montmorillonite, kaolin, mica, and talc. 5 · The copolymerized polymer directly delaminated clay as described in item 1 of the scope of the patent application, wherein the cation-exchange equivalent of the siliceous layered inorganic clay is 50 ~ 200 meq / 100 g 〇6 Nanocrystalline silicon wafers derived from molecular delaminated clay are those obtained by direct delamination of the clay using the copolymerized polymer described in the first item of the patent application scope, and extracted from the metal or soil test by hydroxide or chloride. M silicon wafer. Page 27 593480 VI. Scope of Patent Application 7 · The polymer-based polymer directly delaminated clay-derived nanometer silicon wafers as described in item 6 of the scope of patent application, in which hydroxides or vapors of alkali metals or alkaline earth metals are Sodium hydroxide. 8 · A method for manufacturing direct delaminated clay of copolymerized polymers, which is grafted with polyoxyalkylene amine (polyetheramine) with polypropylene and maleic anhydride (PP-g-ΜΑ) The amphoteric intercalating agent obtained by the polymerization reaction is acidified with an inorganic acid in an organic solvent to form an emulsion, and then mixed with a water-swellable siliceous layered inorganic clay at 60 to 180. 〇 and strong stirring under a reaction system at atmospheric pressure to 50 psig to make it emulsify intercalation reaction in water to obtain a fully delaminated copolymerized polymer directly delaminated. 9 · As described in item 8 of the scope of patent application The manufacturing method, in which the Moire number of the amphoteric intercalating agent and the cation exchange equivalent of the silica-layer inorganic clay is 1: 3 ~ 2: 1. The manufacturing method according to item 8 of the scope of patent application, wherein the organic saturated hydrocarbons and aromatic ^ 6-days, nitriles, saturated hydrocarbons, tritium, tritium: 丨: ° 8th of the scope of patents According to the manufacturing method, there are methyl isobutyl ketone, sodium, diisopropyl ether, methyl third butyl ether, cyclohexane, ethyl acetate, pentane, and hexane. The production method of the layered inorganic clay system described in the fourth aspect, wherein the silicon, (kaolU) , With mother Γ · montmorillonite, kaolin .; τ mother (WCa) and talc (talc). 593480 VI. Application for patent scope 1 3 · Manufacturing method as described in item 8 of the scope of patent application Among them, the cationic cross-equivalent equivalent of the siliceous layered inorganic clay is 50 ~ 20,011,169,800. 1 4 · The manufacturing method according to item 8 of the scope of patent application, wherein the polyetheramine is Selected from polyoxypropylene diamine, polyethyl oxamine diamine, poly (ethyl ether-propyl scale) ) Diamine pOly (〇Xyethylene ~ 〇xypropylene) diamine adduct ° 1 5. The manufacturing method as described in item 8 of the scope of patent application, wherein the inorganic acid is selected from the group consisting of hydrochloric acid, sulfuric acid, filling acid, and acid. 16. The manufacturing method as described in item 8 of the scope of patent application, wherein the amphoteric intercalating agent is acidified with an inorganic acid in an organic solvent to form an emulsion, and then mixed with water-swelled siliceous layered inorganic clay, at 80 ~ 160 ° C and 14.7 to The 50 Ops ig reaction system was stirred vigorously to perform an emulsification intercalation reaction in water to obtain a fully delaminated copolymerized polymer and directly delaminated clay. 17. The manufacturing method as described in item 8 of the scope of patent application, wherein the amphoteric intercalating agent is acidified with an inorganic acid in an organic solvent to form an emulsion, and ^ is mixed with a water-swellable siliceous layered inorganic clay. 〇 ~ 12〇 It and Η 7 ~ under strong agitation under the system to emulsify intercalation in water reaction system to completely delaminate the copolymer directly delaminated clay. 1 8 · = The manufacturing method described in item 8 of the scope of patent application, which ^ I-copolymer molecules directly delaminated clay system as the application of w lacquer. τ 1 The horse oil industry 〖1 9 · = The manufacturing method described in item 8 of the scope of the patent application, which is a compound of "molecular direct delamination clay system as polymer 593480 Scope of patent application Application of material modifier. 〇 · The production method of the clay-derived nano-stone slabs derived from the copolymerized molecules directly delaminated is the copolymerized high-secondary grade obtained by using the method in the scope of patent application No. 8 = directly delaminated clay and dissolved in a specific temperature Organic solvent to form the lead 4A; and then disperse the Shixi oxygen layered inorganic clay in hot water and stir vigorously to form the slurry B; and then mix the slurry A and the slurry β, and stir at a specific temperature, Then add an alkali metal or alkaline earth metal hydroxide or chloride aqueous solution to continue vigorous stirring, and after standing still, the nano silicon wafers dispersed in water can be obtained. 21. The manufacturing method as described in item 20 of the scope of patent application, wherein the organic solvent is selected from the group consisting of ethers, ketones, esters, nitriles, saturated hydrocarbons, gasified saturated hydrocarbons, and aromatic hydrocarbons. class. 22. The manufacturing method according to item 20 of the scope of application for a patent, wherein the organic solvent is selected from the group consisting of tetrahydrofuran, diisopropyl, methyl second butyrate, methyl isobutyl, and acetonitrile , Ethyl acetate, pentane, hexane, heptane,% hexane, digasmethane, benzene, toluene, xylene, gaseous benzene, and methoxybenzene. The manufacturing method described in item 20 of the scope of patent application, Among them, the hydroxide or chloride of the alkali metal or alkaline earth metal is sodium hydroxide.