TW531549B - Method for producing thermoplastic nanocomposite - Google Patents

Abstract

A method for producing a thermoplastic nanocomposite is disclosed. The method comprises the steps of: (a) forming a intercalated layered silicate by treating a layered silicate with a polymerizable monomer of an aminoaryl lactam; and (b) melt-blending a thermoplastic polymer with said intercalated layered silicate to form a thermoplastic nanocomposite having the intercalated layered silicate being exfoliated and dispersed in a thermoplastic polymer matrix.

Description

531549

[Field of the invention] The present invention is particularly related to ## 2, a method for preparing plastic nanocomposite materials, and molecular composite materials ^ = ΐ reaction extrusion polymerization, clay delayering dispersion, [Background of the invention] Gold technology's novel nano-composite material manufacturing process. Nano-composite materials Yanba materials fully display the composite ratio of the particle size of the political phase between 1 nm and 100 ⑽, layered reinforcement I: sub-f-level structure Characteristics, such as small particle size, high apparent diameter, low reinforcing material content, etc., are used in automotive cores and tannamic composite materials with low thermal absorption and low water absorption (J :, and have southern strength, high rigidity, and high resistance to dry soil). : Resistance Λ6 composite material (high-purity natural speeding parts and gas barrier packaging film (1 990) and Yueben Qi Chewen #V Mi Nylon 6 composite material (artificial inorganic layer) used in plastic compounding (1 996). Foreign commercial application evaluation A 2 ^ r Nano acrylic coating and nano ^ from Toyota Central Research Institute of Japan, Allied-signal's nylon 6 nano dispersion dispersion blending process development, Japan Showa Denko Corporation MI nylon 66 engineering plastic; USA

Nanocor's Nano PET composites are used in hot-fill bottles and plastics

gum. In the research and development stage, there are ...

Development of catalyst carrier and engineering plastic nanometer dispersion blending process; American GE

Development of a plastics nanometer dispersion blending process for Plastics. The development and application of high-molecular nanocomposite materials' flame retardant properties are currently attracting the attention of all major plastic companies.

531549 V. Description of the invention (2) " " --------- To Tai ^ 2〗 The production process of raw nanocomposite materials generally achieves the effect of layering and dispersion by means of polymerization. In order to achieve the effect of nano-dispersion, the thermoplastic nano-1 2 5 5 is prepared by blending and dispersing process, and the long-chain carbon cationized difluorene ^ oligomer or soluble polymer intercalation is used to swell in the inorganic layered silicon di Dish layer =, to extend the distance between the layers, in order to facilitate the melting and mixing, the molten high I 子 忐 diffuses into the layers, the general effect can only achieve the effect of interstitial swelling II, method to achieve the effect of nano-layer delamination Moreover, the intercalated J-wetting agent used will precipitate and reduce the mechanical properties of the composite material, and the impregnated solvent needs to be excluded during the mixing process. In view of this, the present invention uses a monomer with a reactive rigid molecular chain as an intercalation layer swelling agent. After melting and heating, it polymerizes to form a rigid oligomer or polymer to solve the above problems. [Previous technology] US Pat. No. 5,552,469 swells layered silicate with water-soluble oligomers or high molecular weight intercalation, and then melt-kneads with thermoplastic or thermosetting polymers. The world patent W 0 9 3/0 41 1 7 intercalates and swells the layered silicate with a first or second ammonium salt or a four-stage filling salt, and then melt-kneads it with a thermoplastic polymer.

Japanese Patent Laid-Open No. 8-1 51, 4 4 9 discloses a method for producing an amorphous thermoplastic tree sacral composition, which is made by dissolving an amorphous thermoplastic resin in an organic solvent and intercalating with layered silicic acid. Exhaust gas is melt-kneaded between salt layers. Japanese Patent Laid-Open No. 7-2 0 7, 1 3 4 discloses an aromatic polycarboxylic acid (PC; polycarbonate) resin composition, which is layered; the ε-acid salt layer contains 12 alkane Quaternary ammonium salt intercalated for swelling treatment, and then mixed with pc resin

Page 5 531549 V. Description of Invention (3) Refining. Japanese Patent Laid-Open No. 7-2 2 8, 7 6 2 discloses an aromatic polycarbonate resin composition in which a layered silicate layer is inserted with a quaternary ammonium salt of polyethylene glycol (PEG; polyethylene glycol). The layer is swelled and then kneaded with pC resin. Japanese Patent Application Laid-Open No. 7-3 3 1.02 discloses a thermoplastic resin composition in which a layered silicate layer is swelled with an epoxy-based silane and an organic ammonium salt compound, and then swelled with heat. Plastic resin kneading. Japanese Patent Application Laid-Open No. 8-259, 806 discloses a method and application for producing a polyfluorene resin composition. A layered silicate layer is composed of a tetraethoxysilane-containing (TE0S) compound and caprolactam monoamine. And organic ammonium salt compounds, and then mixed with polyamine resin. Yu gg Ben-kaikai No. 8 2 5 9, 8 4 6 discloses a coated ultra-fine powder = = containing composition and its manufacturing method, the layer is decomposed: ΐΐ agent intercalated to swell, and then with amine monomer Polymerization, = i kneaded with thermoplastic resin. [Summary of the invention] The main purpose of the present invention is you Ae tyi's novel process to prepare for going out of the house: a kind of thermoplastic nano-composite material which is the nano-composite material that achieves the above-mentioned two scattered. In the dry soil layer r [and various types of two = nano-composite materials dispersed by intercalation of reactive monomers. ^: After the base material is pushed and mixed, the necessary steps include 4a) providing a layer of root according to the preparation method of the present invention, wherein the main amine compound reactive monomer is called a secondary salt, and an aromatic amine group is used. Flat body intercalation and swelling treatment; and (b)

$ 6 pages 531549, description of the invention (4) The layered silicate after intercalation and swelling is melt-kneaded with a thermoplastic polymer to obtain a thermoplastic nano-composite material. [Detailed description of the invention] In the present invention, a reactive acid amine monomer is intercalated between silicate layers, and after melting and heating (temperature above 20 ° C), the ring-opening polycondensates to form a rigid molecular chain polymer. The clay layer distance is extended to obtain a delaminated nanometer-scale thermoplastic composite material. In more detail, the present invention intercalates a reactive ammonium monomer between silicate layers, and during melt-kneading processing, polymerizes to form an aromatic polyamine structure with an intermediate point and a terminal functional group. The nano-layer delamination and dispersion effect that achieves the distance between layers is achieved. On the one hand, it has a strong effect of molecular supplementation and the terminal functional groups can react with the polymer base material to be mixed to be compatible. The reactive fluorene monomer of the present invention, the aromatic amine lactam compound 'can be formed by the reaction of an aromatic amino acid and a cyclic lactam compound through the One-step method. The carbon number of the ring system can be from 4 to 18. Examples of reactive amidine monomers include: N_ (p -aminobenzyl) caprolactam, N- (p -aminobenzylmethyl) butyrolactam, n-(P -amine Benzamyl) pentanoylamine, N- (p-aminobenzylmethyl) dodecylamine.

According to the present invention, the layered silicate used is a swelling clay or swelling fluorinated mica mineral having a cation exchange equivalent of 50 to 200 meq / 100g. The swelling clays suitable for the present invention are: smectiie clay, vermiculite, halloysite,

531549

Or sericite, etc .; among them, smectite clay includes montmorillonite, saponite, beidelHte, silicon Nontronite, hectorite, and stevensite. Swellable fluorinated mica suitable for this Maoming can be mixed with at least one of g 0 ~ 65 wt% talc (^ & 1 c) spot 10 ~ 35 wt% silicon fluoride, sodium fluoride, and lithium fluoride. Prepared by mouth heating. According to a preferred embodiment of the present invention, the layered silicate used is montmorillonite, which has undergone swelling treatment with amino acid intercalation,

Aminoclay (product of Nanocor).

The process of the present invention can be applied to all crystalline / non-crystalline and polar / non-polar thermoplastic south molecular substrates, such as crystalline and polar Nylon 6 (nylon 6); crystalline and non-polar pp ( Polypropylene); amorphous = non-polar PS (polystyrene); amorphous and polar (polycarbonate), etc. The content of the layered silicate in the composite material is about 0.05 to 80 wt%, preferably 1 to 30 wt%. . In order to make the above and other objects, features, and advantages of the present invention more obvious and easy II ', the following describes the car driver's best embodiment, and in conjunction with the accompanying drawings, the detailed description is as follows: [Simplified description of the drawings]

Figure 1 shows Aminoclay-amidamine monomer complex and Nylon 6 in different ratios (a) 1 wt%, (b) 2 wt%; (c) 5 wt%; (d) 10 wt ° /. Kneaded by kneader and (e) XRD pattern of Aminoclay-amidamine monomer complex. Figure 2 shows the Aminoclay-amine compound and pp resin in different proportions (a) 1 wt%, (b) 2 wt%; (c) 5 wt%; (d) 10 wt% after kneading

Page 8 531549 V. Description of the invention (6) Organic compounding and (e) XRD pattern of Aminoclay-amine compound. Figure 3 shows Aminoclay-amidamine monomer composite and PS resin in different ratios (a) 1 wt%; (b) 2 wt%; (c) 5 wt%; (d) 10 wt%. (E) XRD pattern of Aminoclay-amidamine monomer complex. Figure 4 shows Ami noclay-amidamine monomer composite and PC resin in different proportions (a) 1 wt%; (b) 2 wt%; (c) 5 wt%; (d) 10 wt%. And (e) the XRD pattern of the Aminoclay-acid amine monomer complex. [Example] Synthesis of reactive amidine monomer

Put 100 g (0.703 mol) p-aminobenzoic acid and 385 ml (5.370 mol) of thionyl chloride in a 1000 ml round bottom bottle, and connect the round bottom bottle with serpentine condensation Tube, and introduce a saturated aqueous sodium hydroxide solution to neutralize the HC1 produced, and stir under reflux for 4 hours until the turbid solution becomes clear. The solution was transferred to a pear-shaped bottle, and concentrated under reduced pressure to remove excess unreacted thionyl chloride, and then distilled under reduced pressure to obtain p-sulfinylaminobenzyl chloride (p-sulfinylaminobenz〇yl).

chloride) 'collected and stored in a nitrogen sealed container. In a 3,000 ml = neck flask, 150 g (0.730 mol) of caprolactam, 1300 mi formamidine, and 680 ml of pyridine were placed, and nitrogen was passed through and stirred. The solution was added to the solution under an ice bath. 147 · 1 g (.730 mol) of p-thionylaminoaminobenzene, stir the reaction, slowly warm to room temperature, stir the reaction for 14 hours, remove the pyridine chloride by filtration, and 5% sodium bicarbonate aqueous solution Extracted and washed twice, concentrated under reduced pressure to remove the solvent, and the product was recrystallized twice from ethyl acetate to obtain a reaction.

Page 9 531549 V. Description of the invention (7) N- (p-aminobenzyl) caprolactam [N-(^-aminobenzoy1) caprolactam] ° of thermoplastic amide monomer 〖$ The reactive monomer N- (p-aminophenylphenyl) caprolactone synthesized above and Aminoclay (Nanocor's product, 12-ami no 1 auric acid) Layer swelled organic montmorillonite) in a weight ratio of 1: 1 in a mixture of pyridine solvents and added 0.5 8 phr of 4- (dimethylamino) σ specific ratio [4- (dimethylamino ) pyridine;

DMAP)] as a hydrazine exchange catalyst. After being stirred and mixed uniformly, the pyridine solvent was removed under vacuum. The obtained composites were different from the representative ones at different weight ratios (丨, 2, 5, 10 wt%). Thermoplastic polymer substrate, including crystalline and polar Ny 1 on 6 (nylon 6); crystalline and non-polar pp (polypropylene); amorphous and non-polar p S (polystyrene) ); Amorphous and polar PC (polycarbonate), kneaded and dispersed in a kneader, the XRD test spectra of the obtained composite material after hot pressing into flakes are shown in Figures 1 to 4 Nylon 6, PP, PS can achieve the effect of nano-layer delamination and dispersion when the content of reactive clay monomer intercalated organic clay compound is less than 5 wt% (PC is less than 10 wt%) (XRD spectrum is 2 / 9: 2.0. There is no diffraction peak between ~ 10.0.). The results show that the organoclay composites intercalated with this reactive monomer have great industrial application value in the preparation of thermoplastic nanocomposites by the blending process. Although the present invention has been disclosed as above with a preferred embodiment, it is not intended to limit the present invention. Any person skilled in the art can make various modifications and retouches without departing from the spirit and scope of the present invention. Therefore, the present invention Protection

531549 V. Description of invention (8) The scope shall be determined by the scope of the attached patent application.

Claims (1)

Case No. 531549 88108289 Sixth, the method of applying for a patent application includes the following steps: (a) Put the methyl and thionylamine gas in a reaction bottle and heat it under reflux, and then distill under reduced pressure to obtain p- thionylamino group. Phenylhydrazone gas (b) Pass the caprolactam and co-solvent solution under nitrogen, add P-thiosulfenylaminobenzyl chloride under an ice bath and stir, and react at a temperature of 10 to 300 ° C. ~ 20 hours, after filtration, washing, concentration and purification under reduced pressure, the reactive amidine monomer N- (p-aminophenylphenyl) caprolactam (c) can be provided as a layer of silicic acid Salt, intercalated and swelled with an aromatic amine 1 · methylpyridamine compound reactive monomer; and (d) melting and mixing the layered silicate after intercalated and swelled with a thermoplastic polymer, The thermoplastic polymer is selected from polyamide, polyolefin, polyester, and polystyrene to obtain a thermoplastic nano composite material. 2. The method according to item 1 of the scope of the patent application, wherein the reactive amine brewing monomer is formed by reacting an aromatic amino acid and a cyclic lactam compound. 3. The method according to item 2 of the scope of the patent application, wherein the carbon number of the cyclic system of the cyclic lactam compound is 4 to 8. 4. The method according to item 3 of the scope of the patent application, wherein the reactive amine brewing monomer is N- (p-aminophenylphenyl) caprolactone. 5. The preparation method according to item 1 of the scope of patent application, wherein the cation exchange equivalent of the layered silicate is 50 to 200 meq / 100 g. 6. The preparation method as described in item 1 of the scope of application for a patent, wherein the content of the layered oxalate in the composite material is from 0.5 to 80 WtG / 〇. 7. The preparation method as described in the first paragraph of the patent application park, wherein the layered silicate is selected from the group consisting of: alumite clay 531549 __ Case No. 88108289_ Che Yue Yue π ______ Sixth, the scope of patent applications (smectite clay), vermiculite, tubular kaolin (halloysite), and sericite (sericite). 8. The preparation method as described in item 7 of the scope of the patent application, wherein the smectite clay is selected from the group consisting of montmorillonite, saponite, rich Bemontllite, nontronite, hectorite, and stevensite ° ° 9 · Preparation method as described in the scope of the patent application No. 1 The silicate is an amino acid intercalated swelling treatment Montmorillonite. 10. According to the preparation method described in item 1 of the scope of patent application, the sonic silicate in beans is fluorinated mica. Wanyun /, T 4 Guang11 · The fluorinated mica described in the scope of application for patent No. 丨 0 is a method of preparing 90 ~ 65wt% talc, / Zhongshi Shixi, Jiuhuana, and Fluoride Zhongqi ; With 10 ~ 35 fluorination. Species, prepared by mixing and heating, and 1 2 · As described in the scope of the patent application | Plastic polymer is selected from the following preparation methods =, wherein the heat resistant 66 (Ny 1〇η66), polyethylene (PE ),》 Groups ·· Nylon 6 (Ny 1οη6), (PC), Poly (terephthalate) 6- (pET) 1 ^ Endene (PP), Polycarbonate (PBT), Polystyrene (PS), Polypropylene polybutylene terephthalate_butadiene-styrene (ABS). $ 15 pages