CN1523060A - A kind of exfoliation polymer/montmorillonite nanocomposite material and preparation method thereof - Google Patents

Abstract

The invention belongs to an exfoliated polymer/montmorillonite nanocomposite material and a preparation method thereof. Polymers of choice are polyamide, anhydrided polypropylene, anhydrided polyethylene, polyurethane, polystyrene, anhydrided ethylene propylene rubber, nitrile rubber, styrene butadiene rubber or silicone rubber or blends polypropylene/polyamide , polypropylene/anhydrided polypropylene, polyethylene/anhydrided polyethylene, polyamide/anhydrided polypropylene or polyurethane/anhydrided polypropylene; organically modified montmorillonite is composed of montmorillonite, cation exchanger primary amine, secondary Ammonium or tertiary ammonium, the amount of modifier is strictly limited below the ion exchange capacity of montmorillonite, and then the polymer and modified montmorillonite are directly melt-mixed to obtain exfoliated polymer/montmorillonite nanoparticles composite material.

Description

A kind of exfoliation polymer/montmorillonite nanocomposite material and preparation method thereof

technical field

The invention belongs to a stripping polymer/montmorillonite nanocomposite material; the invention also relates to a preparation method of a stripping polymer/montmorillonite nanocomposite material.

Background technique

Using a small amount of one-dimensional nano-sized layered inorganic components to modify the polymer can significantly improve the rigidity and strength of the polymer, while the specific gravity and transparency of the material are basically unchanged compared with the polymer, and can also greatly improve the polymerization. Thermal stability, flame retardancy and barrier properties of materials. The effective exfoliation and dispersion of montmorillonite in the polymer plays a key role in improving the performance of the material.

There are many methods for the preparation of polymer/montmorillonite nanocomposites, among which the melting method is considered to be the most promising because it can use traditional polymer processing or extrusion equipment and has no environmental pollution. Compatible with most polymers. It is generally believed that the organic modification of montmorillonite is the premise of the melting method, and its purpose is to change the hydrophilicity of the surface of montmorillonite and provide a more favorable environment for polymer molecules or monomers to enter the interlayer gap of montmorillonite. lipophilic environment. Yui, T. et al. think (Langmuir 2002, 18, 891) that a large amount of ammonium ion surfactant should be used to modify montmorillonite, so as to replace the inorganic cations between the montmorillonite layers as much as possible or increase the montmorillonite basic layer spacing. In related patents CN1267682A and CN1247206A, an excessive amount of modifying agent is used to prepare organic montmorillonite. However, we found in our work that the peeling of the montmorillonite layer depends on the good interaction between the montmorillonite and the polymer, and the use of more modifiers in the modified montmorillonite will increase the gap between the montmorillonite layers. The density of the modifier prevents the polymer from entering the montmorillonite layer or weakens the interaction between the polymer and the montmorillonite, which is not conducive to the dispersion of the montmorillonite.

Contents of the invention

The object of the present invention is to provide a kind of exfoliation polymer/montmorillonite nanocomposite material;

Another object of the present invention is to provide a preparation method of exfoliated polymer/montmorillonite nanocomposite material.

In the present invention, the amount of cationic modifier is strictly limited below the ion exchange capacity (CEC) of montmorillonite, and then the polymer is directly melt-mixed with the modified montmorillonite to obtain polymer/montmorillonite with an exfoliated structure nanocomposites.

The polymers prepared in the present invention are polyamide 6, polyamide 66, polyamide 11, polyamide 12, polyamide 1010, anhydrided polypropylene, anhydrided polyethylene, polyurethane, polystyrene, anhydrided ethylene Acrylic rubber, nitrile rubber, styrene-butadiene rubber or silicone rubber polymers or polymer blends polypropylene/polyamide 11, polypropylene/polyamide 12, polypropylene/anhydrided polypropylene, polyethylene/anhydrided polyethylene, Polyamide 6/Anhydrided Polypropylene, Polyamide 66/Anhydrided Polypropylene, Polyamide 11/Anhydrided Polypropylene, Polyamide 12/Anhydrided Polypropylene, Polyamide 1010/Anhydrided Polypropylene or Polyurethane/Anhydride Polypropylene; organic montmorillonite is composed of the following components: 16-40 grams of montmorillonite in parts by weight, and 3.8-19.2 grams of primary amine, swollen ammonium or tertiary ammonium as a cation exchanger; the medium water for dispersing montmorillonite is 500-1500ml, medium water for dispersing cation exchangers 100-500ml; ratio of moles of cation modifier to ion exchange capacity of montmorillonite is less than 1;

The preparation steps are as follows:

16-40 grams of montmorillonite with a cation exchange capacity of 50-150meq/100g is stirred in 500-1000ml of deionized water by weight for 0.5-2 hours at high speed to form a stable suspension system, and 0.2CEC-1.0CEC Add the cation exchanger to 100-500ml of deionized water at a temperature of 60-90°C, add equimolar protonating agent hydrochloric acid or sulfuric acid, and emulsify at high speed to form a uniformly dispersed emulsion, and add it to the suspension system of the above-mentioned montmorillonite. Mix under high-speed stirring for 10 to 60 minutes, precipitate, filter, vacuum dry and pulverize to obtain organic montmorillonite, and the weight ratio of polymer or blended polymer to modified montmorillonite is 50 to 99 parts: 1～ 50 parts; In traditional polymer mixing or extrusion equipment, the polymer and organic montmorillonite are melted and intercalated respectively to obtain exfoliated polymer/montmorillonite nanocomposites directly.

The process of the invention is simple and easy to implement, does not need to add additional equipment, has low production input cost, quick effect and is easy to popularize.

Detailed ways

Example 1

24 grams of montmorillonite with a cation exchange capacity of 120meq/100g was stirred in 500ml of deionized water at high speed for 0.5h to form a stable suspension system. Add 17.3 grams of cation exchanger octadecylamine to 500 ml of deionized water, add equimolar protonating agent hydrochloric acid, and emulsify at a high speed to form a uniformly dispersed emulsion. The suspension and emulsion heated to 60° C. were mixed under high-speed stirring for 10 minutes, precipitated, filtered, vacuum-dried and pulverized to obtain organic montmorillonite (OM1). Melt intercalation of polyurethane and organic montmorillonite in traditional polymer mixing or extrusion equipment to directly obtain polymer/montmorillonite nanocomposite PUS1, its wide-angle X-ray results (see attached table 1) It shows that PUS1 has an exfoliated structure. Change the dosage of cation exchanger to be 1.0CEC, 1.5CEC, 2.0CEC, 2.5CEC respectively, namely respectively 28.8 grams, 43.2 grams, 57.6 grams and 72 grams, and prepare corresponding polyurethane/montmorillonite nanocomposite PUS2, The results of PUS3, PUS4, and PUS5 are shown in Table 1. Compare their structures and mechanical properties, see the accompanying drawings.

Table 1

Name Polyurethane PUS1 PUS2 PUS3 PUS4 PUS5

Tensile Strength

29.9 29.5 33.2 31.9 29.6 30.6

(MPa)

elongation at break

270 255 330 273 297 280

Rate(%)

Stretch elasticity

242 652 608 557 543 523

Modulus (MPa)

Example 2

40 grams of montmorillonite with a cation exchange capacity of 50 meq/100 g was stirred in 1000 ml of deionized water at high speed for 1 hour to form a stable suspension system. Add 12 grams of cation exchanger cetyltrimethylammonium bromide into 200 ml of deionized water, add equimolar protonating agent sulfuric acid, and emulsify at high speed to form a uniformly dispersed emulsion. The suspension and emulsion heated to 80° C. were mixed under high-speed stirring for 30 minutes, precipitated, filtered, vacuum-dried and pulverized to obtain organic montmorillonite. Melt intercalation of polyamide 6 and organic montmorillonite in traditional polymer mixing or extrusion equipment to directly obtain polymer/montmorillonite nanocomposites, the (001 ) diffraction peaks disappear, indicating that montmorillonite is well dispersed in these polymers and has an exfoliated structure.

Example 3

16 grams of montmorillonite with a cation exchange capacity of 150 meq/100 g was stirred in 1000 ml of deionized water at high speed for 2 hours to form a stable suspension system. Add 14.4 grams of cation exchanger cetyltrimethylammonium bromide to 300 ml of deionized water, add equimolar protonating agent sulfuric acid, and emulsify at high speed to form a uniformly dispersed emulsion. The suspension and emulsion heated to 90° C. were mixed under high-speed stirring for 60 minutes, precipitated, filtered, vacuum-dried and pulverized to obtain organic montmorillonite. Melt intercalation of polyamide 66 and organic montmorillonite in traditional polymer mixing or extrusion equipment to directly obtain polymer/montmorillonite nanocomposites, the (001 ) diffraction peaks disappear, indicating that montmorillonite is well dispersed in these polymers and has an exfoliated structure.

Example 4

16 grams of montmorillonite with a cation exchange capacity of 120meq/100g was stirred in 1000ml of deionized water at high speed for 2 hours to form a stable suspension system. Respectively 0.2, 0.4, 0.6, 0.8 and 1.0 times of CEC quantity of cation exchanger octadecylamine (its weight is respectively 3.8 grams, 7.7 grams, 11.5 grams, 15.4 grams and 19.2 grams) are respectively added in 500ml deionized water, and then Add equimolar protonating agent hydrochloric acid to emulsify at high speed to form a uniformly dispersed emulsion. The suspension and emulsion heated to 60° C. were mixed under high-speed stirring for 30 minutes, precipitated, filtered, vacuum-dried and pulverized to obtain organic montmorillonite. Melt intercalation of anhydrided polypropylene and organic montmorillonite in traditional polymer mixing or extrusion equipment to directly obtain a series of anhydrided polypropylene/montmorillonite nanocomposites, the X-ray spectrum of which is The (001) diffraction peaks of the exfoliated clays all disappeared, indicating that the montmorillonites were well dispersed in these polymers and had an exfoliated structure.

Example 5

14 grams of montmorillonite with a cation exchange capacity of 150 meq/100 g was stirred in 1500 ml of deionized water at high speed for 2 hours to form a stable suspension system. Add 10.5 grams of cation exchanger cetyltrimethylammonium bromide into 500 ml of deionized water, add equimolar protonating agent sulfuric acid, and emulsify at high speed to form a uniformly dispersed emulsion. The suspension and emulsion heated to 90° C. were mixed under high-speed stirring for 50 minutes, precipitated, filtered, vacuum-dried and pulverized to obtain organic montmorillonite. In traditional polymer mixing or extrusion equipment, the organic montmorillonite is melt-mixed with polyamide 11, and the polymer/montmorillonite nanocomposite is obtained accordingly, and the (001 ) diffraction peaks disappear, indicating that montmorillonite is well dispersed in these polymers and has an exfoliated structure.

Example 6

14 grams of montmorillonite with a cation exchange capacity of 150 meq/100 g was stirred in 1500 ml of deionized water at high speed for 2 hours to form a stable suspension system. Add 10.5 grams of cation exchanger cetyltrimethylammonium bromide into 500 ml of deionized water, add equimolar protonating agent sulfuric acid, and emulsify at high speed to form a uniformly dispersed emulsion. The suspension and emulsion heated to 90° C. were mixed under high-speed stirring for 50 minutes, precipitated, filtered, vacuum-dried and pulverized to obtain organic montmorillonite. In traditional polymer mixing or extrusion equipment, the organic montmorillonite is melt-mixed with polyamide 12, and the polymer/montmorillonite nanocomposite is obtained accordingly, and the (001 ) diffraction peaks disappear, indicating that montmorillonite is well dispersed in these polymers and has an exfoliated structure.

Example 7

14 grams of montmorillonite with a cation exchange capacity of 150 meq/100 g was stirred in 1500 ml of deionized water at high speed for 2 hours to form a stable suspension system. Add 10.5 grams of cation exchanger cetyltrimethylammonium bromide into 500 ml of deionized water, add equimolar protonating agent sulfuric acid, and emulsify at high speed to form a uniformly dispersed emulsion. The suspension and emulsion heated to 90° C. were mixed under high-speed stirring for 50 minutes, precipitated, filtered, vacuum-dried and pulverized to obtain organic montmorillonite. Melt mixing organic montmorillonite with polyamide 1010 in conventional polymer mixing or extrusion equipment to obtain polymer/montmorillonite nanocomposites correspondingly, the (001 ) diffraction peaks disappear, indicating that montmorillonite is well dispersed in these polymers and has an exfoliated structure.

Example 8

14 grams of montmorillonite with a cation exchange capacity of 150 meq/100 g was stirred in 1500 ml of deionized water at high speed for 2 hours to form a stable suspension system. Add 10.5 grams of cation exchanger cetyltrimethylammonium bromide into 500 ml of deionized water, add equimolar protonating agent sulfuric acid, and emulsify at high speed to form a uniformly dispersed emulsion. The suspension and emulsion heated to 90° C. were mixed under high-speed stirring for 50 minutes, precipitated, filtered, vacuum-dried and pulverized to obtain organic montmorillonite. In traditional polymer mixing or extrusion equipment, organic montmorillonite is melt-mixed with anhydrided polyethylene to obtain polymer/montmorillonite nanocomposites, and the X-ray spectrum of montmorillonite ( 001) diffraction peaks all disappear, indicating that montmorillonite is well dispersed in these polymers and has an exfoliated structure.

Example 9

14 grams of montmorillonite with a cation exchange capacity of 150 meq/100 g was stirred in 1500 ml of deionized water at high speed for 2 hours to form a stable suspension system. Add 10.5 grams of cation exchanger cetyltrimethylammonium bromide into 500 ml of deionized water, add equimolar protonating agent sulfuric acid, and emulsify at high speed to form a uniformly dispersed emulsion. The suspension and emulsion heated to 90° C. were mixed under high-speed stirring for 50 minutes, precipitated, filtered, vacuum-dried and pulverized to obtain organic montmorillonite. In traditional polymer mixing or extrusion equipment, the organic montmorillonite is melt-mixed with polystyrene, and the polymer/montmorillonite nanocomposite is obtained accordingly, and the (001 ) diffraction peaks disappear, indicating that montmorillonite is well dispersed in these polymers and has an exfoliated structure.

Example 10

14 grams of montmorillonite with a cation exchange capacity of 150 meq/100 g was stirred in 1500 ml of deionized water at high speed for 2 hours to form a stable suspension system. Add 10.5 grams of cation exchanger cetyltrimethylammonium bromide into 500 ml of deionized water, add equimolar protonating agent sulfuric acid, and emulsify at high speed to form a uniformly dispersed emulsion. The suspension and emulsion heated to 90° C. were mixed under high-speed stirring for 50 minutes, precipitated, filtered, vacuum-dried and pulverized to obtain organic montmorillonite. In traditional polymer mixing or extrusion equipment, organic montmorillonite and anhydrided ethylene-propylene rubber are melt-mixed to obtain polymer/montmorillonite nanocomposites, and the X-ray spectrum of montmorillonite is (001) diffraction peaks all disappear, indicating that montmorillonite is well dispersed in these polymers and has an exfoliated structure.

Example 11

14 grams of montmorillonite with a cation exchange capacity of 150 meq/100 g was stirred in 1500 ml of deionized water at high speed for 2 hours to form a stable suspension system. Add 10.5 grams of cation exchanger cetyltrimethylammonium bromide into 500 ml of deionized water, add equimolar protonating agent sulfuric acid, and emulsify at high speed to form a uniformly dispersed emulsion. The suspension and emulsion heated to 90° C. were mixed under high-speed stirring for 50 minutes, precipitated, filtered, vacuum-dried and pulverized to obtain organic montmorillonite. In traditional polymer mixing or extrusion equipment, organic montmorillonite is melt-mixed with nitrile rubber to obtain polymer/montmorillonite nanocomposites accordingly. The (001) of montmorillonite in its X-ray spectrum ) diffraction peaks disappear, indicating that montmorillonite is well dispersed in these polymers and has an exfoliated structure.

Example 12

14 grams of montmorillonite with a cation exchange capacity of 150 meq/100 g was stirred in 1500 ml of deionized water at high speed for 2 hours to form a stable suspension system. Add 10.5 grams of cation exchanger cetyltrimethylammonium bromide into 500 ml of deionized water, add equimolar protonating agent sulfuric acid, and emulsify at high speed to form a uniformly dispersed emulsion. The suspension and emulsion heated to 90° C. were mixed under high-speed stirring for 50 minutes, precipitated, filtered, vacuum-dried and pulverized to obtain organic montmorillonite. In traditional polymer mixing or extrusion equipment, organic montmorillonite and styrene-butadiene rubber are melt-mixed to obtain polymer/montmorillonite nanocomposites accordingly, and the (001 ) diffraction peaks disappear, indicating that montmorillonite is well dispersed in these polymers and has an exfoliated structure.

Example 13

14 grams of montmorillonite with a cation exchange capacity of 150 meq/100 g was stirred in 1500 ml of deionized water at high speed for 2 hours to form a stable suspension system. Add 10.5 grams of cation exchanger cetyltrimethylammonium bromide into 500 ml of deionized water, add equimolar protonating agent sulfuric acid, and emulsify at high speed to form a uniformly dispersed emulsion. The suspension and emulsion heated to 90° C. were mixed under high-speed stirring for 50 minutes, precipitated, filtered, vacuum-dried and pulverized to obtain organic montmorillonite. In traditional polymer mixing or extrusion equipment, organic montmorillonite is melt-mixed with silicone rubber polymers to obtain polymer/montmorillonite nanocomposites accordingly, and the ( 001) diffraction peaks all disappear, indicating that montmorillonite is well dispersed in these polymers and has an exfoliated structure.

Example 14

40 grams of montmorillonite with a cation exchange capacity of 50 meq/100 g was stirred in 1000 ml of deionized water at high speed for 1 hour to form a stable suspension system. Add 12 grams of cation exchanger cetyltrimethylammonium bromide into 200 ml of deionized water, add equimolar protonating agent sulfuric acid, and emulsify at high speed to form a uniformly dispersed emulsion. The suspension and emulsion heated to 80° C. were mixed under high-speed stirring for 30 minutes, precipitated, filtered, vacuum-dried and pulverized to obtain organic montmorillonite. In traditional polymer mixing or extrusion equipment, 89 parts of polypropylene, 10 parts of polyamide 11 and 1 part of organic montmorillonite were melt-intercalated to obtain polymer/montmorillonite nanocomposites directly. The X-ray The (001) diffraction peaks of montmorillonite in the spectrum disappear, indicating that montmorillonite is well dispersed in these polymers and has an exfoliated structure.

Example 15

16 grams of montmorillonite with a cation exchange capacity of 150 meq/100 g was stirred in 1000 ml of deionized water at high speed for 2 hours to form a stable suspension system. Add 14.4 grams of cation exchanger cetyltrimethylammonium bromide to 300 ml of deionized water, add equimolar protonating agent sulfuric acid, and emulsify at high speed to form a uniformly dispersed emulsion. The suspension and emulsion heated to 90° C. were mixed under high-speed stirring for 60 minutes, precipitated, filtered, vacuum-dried and pulverized to obtain organic montmorillonite. In traditional polymer mixing or extrusion equipment, 80 parts of polypropylene, 15 parts of polyamide 12 and 10 parts of organic montmorillonite were melt-intercalated to obtain polymer/montmorillonite nanocomposites directly. The X-ray The (001) diffraction peaks of montmorillonite in the spectrum disappear, indicating that montmorillonite is well dispersed in these polymers and has an exfoliated structure.

Example 16

16 grams of montmorillonite with a cation exchange capacity of 120meq/100g was stirred in 1000ml of deionized water at high speed for 2 hours to form a stable suspension system. Add 3.8 grams of cation exchanger octadecylamine to 500 ml of deionized water, add equimolar protonating agent hydrochloric acid, emulsify at high speed, and form a uniformly dispersed emulsion. The suspension and emulsion heated to 60° C. were mixed under high-speed stirring for 30 minutes, precipitated, filtered, vacuum-dried and pulverized to obtain organic montmorillonite. Melt intercalation of 80 parts of polypropylene, 15 parts of anhydrided polypropylene and 5 parts of organic montmorillonite in traditional polymer mixing or extrusion equipment to directly obtain a series of anhydrided polypropylene/montmorillonite nanocomposites , the (001) diffraction peaks of montmorillonite in its X-ray spectrum disappeared, indicating that montmorillonite was well dispersed in these polymers and had an exfoliated structure.

Example 17

14 grams of montmorillonite with a cation exchange capacity of 150 meq/100 g was stirred in 1500 ml of deionized water at high speed for 2 hours to form a stable suspension system. Add 10.5 grams of cation exchanger cetyltrimethylammonium bromide into 500 ml of deionized water, add equimolar protonating agent sulfuric acid, and emulsify at high speed to form a uniformly dispersed emulsion. The suspension and emulsion heated to 90° C. were mixed under high-speed stirring for 50 minutes, precipitated, filtered, vacuum-dried and pulverized to obtain organic montmorillonite. In traditional polymer mixing or extrusion equipment, 5 parts of organic montmorillonite, 60 parts of polyethylene, and 35 parts of anhydrided polyethylene are melt-mixed to obtain polymer/montmorillonite nanocomposites, and their X- The (001) diffraction peaks of montmorillonite in the ray spectra all disappear, indicating that montmorillonite is well dispersed in these polymers and has an exfoliated structure.

Example 18

14 grams of montmorillonite with a cation exchange capacity of 150 meq/100 g was stirred in 1500 ml of deionized water at high speed for 2 hours to form a stable suspension system. Add 10.5 grams of cation exchanger cetyltrimethylammonium bromide into 500 ml of deionized water, add equimolar protonating agent sulfuric acid, and emulsify at high speed to form a uniformly dispersed emulsion. The suspension and emulsion heated to 90° C. were mixed under high-speed stirring for 50 minutes, precipitated, filtered, vacuum-dried and pulverized to obtain organic montmorillonite. In traditional polymer mixing or extrusion equipment, 10 parts of organic montmorillonite is melt-mixed with 70 parts of polyamide 6 and 20 parts of anhydrided polypropylene to obtain polymer/montmorillonite nanocomposites correspondingly, whose X The (001) diffraction peaks of montmorillonite in the -ray spectra all disappeared, indicating that montmorillonite was well dispersed in these polymers and had an exfoliated structure.

Example 19

14 grams of montmorillonite with a cation exchange capacity of 150 meq/100 g was stirred in 1500 ml of deionized water at high speed for 2 hours to form a stable suspension system. Add 10.5 grams of cation exchanger cetyltrimethylammonium bromide into 500 ml of deionized water, add equimolar protonating agent sulfuric acid, and emulsify at high speed to form a uniformly dispersed emulsion. The suspension and emulsion heated to 90° C. were mixed under high-speed stirring for 50 minutes, precipitated, filtered, vacuum-dried and pulverized to obtain organic montmorillonite. In traditional polymer mixing or extrusion equipment, 5 parts of organic montmorillonite are melt-mixed with 80 parts of polyamide 66 and 15 parts of anhydrided polypropylene to obtain polymer/montmorillonite nanocomposites correspondingly, whose X The (001) diffraction peaks of montmorillonite in the -ray spectra all disappeared, indicating that montmorillonite was well dispersed in these polymers and had an exfoliated structure.

Example 20

14 grams of montmorillonite with a cation exchange capacity of 150 meq/100 g was stirred in 1500 ml of deionized water at high speed for 2 hours to form a stable suspension system. Add 10.5 grams of cation exchanger cetyltrimethylammonium bromide into 500 ml of deionized water, add equimolar protonating agent sulfuric acid, and emulsify at high speed to form a uniformly dispersed emulsion. The suspension and emulsion heated to 90° C. were mixed under high-speed stirring for 50 minutes, precipitated, filtered, vacuum-dried and pulverized to obtain organic montmorillonite. In traditional polymer mixing or extrusion equipment, 10 parts of organic montmorillonite is melt-mixed with 60 parts of polyamide 11 and 30 parts of anhydrided polypropylene to obtain polymer/montmorillonite nanocomposites correspondingly, its X The (001) diffraction peaks of montmorillonite in the -ray spectra all disappeared, indicating that montmorillonite was well dispersed in these polymers and had an exfoliated structure.

Example 21

14 grams of montmorillonite with a cation exchange capacity of 150 meq/100 g was stirred in 1500 ml of deionized water at high speed for 2 hours to form a stable suspension system. Add 10.5 grams of cation exchanger cetyltrimethylammonium bromide into 500 ml of deionized water, add equimolar protonating agent sulfuric acid, and emulsify at high speed to form a uniformly dispersed emulsion. The suspension and emulsion heated to 90° C. were mixed under high-speed stirring for 50 minutes, precipitated, filtered, vacuum-dried and pulverized to obtain organic montmorillonite. In traditional polymer mixing or extrusion equipment, 15 parts of organic montmorillonite is melt-mixed with 55 parts of polyamide 12 and 30 parts of anhydrided polypropylene to obtain polymer/montmorillonite nanocomposites correspondingly, its X The (001) diffraction peaks of montmorillonite in the -ray spectra all disappeared, indicating that montmorillonite was well dispersed in these polymers and had an exfoliated structure.

Example 22

14 grams of montmorillonite with a cation exchange capacity of 150 meq/100 g was stirred in 1500 ml of deionized water at high speed for 2 hours to form a stable suspension system. Add 10.5 grams of cation exchanger cetyltrimethylammonium bromide into 500 ml of deionized water, add equimolar protonating agent sulfuric acid, and emulsify at high speed to form a uniformly dispersed emulsion. The suspension and emulsion heated to 90° C. were mixed under high-speed stirring for 50 minutes, precipitated, filtered, vacuum-dried and pulverized to obtain organic montmorillonite. In traditional polymer mixing or extrusion equipment, 8 parts of organic montmorillonite are melt-mixed with 68 parts of polyamide 1010 and 24 parts of anhydrided polypropylene to obtain polymer/montmorillonite nanocomposites correspondingly, whose X The (001) diffraction peaks of montmorillonite in the -ray spectra all disappeared, indicating that montmorillonite was well dispersed in these polymers and had an exfoliated structure.

Example 23

14 grams of montmorillonite with a cation exchange capacity of 150 meq/100 g was stirred in 1500 ml of deionized water at high speed for 2 hours to form a stable suspension system. Add 10.5 grams of cation exchanger cetyltrimethylammonium bromide into 500 ml of deionized water, add equimolar protonating agent sulfuric acid, and emulsify at high speed to form a uniformly dispersed emulsion. The suspension and emulsion heated to 90° C. were mixed under high-speed stirring for 50 minutes, precipitated, filtered, vacuum-dried and pulverized to obtain organic montmorillonite. In traditional polymer mixing or extrusion equipment, 6 parts of organic montmorillonite are melt-mixed with 76 parts of polyurethane and 18 parts of anhydrided polypropylene to obtain polymer/montmorillonite nanocomposites correspondingly, whose X The (001) diffraction peaks of montmorillonite in the -ray spectra all disappeared, indicating that montmorillonite was well dispersed in these polymers and had an exfoliated structure.

Claims (4)

1. one kind prepares exfoliated polymer and Nano composite material of montmorillonite, and polymkeric substance is a polyamide 6, polyamide 66, polymeric amide 11, polymeric amide 12, polyamide 1010, the acid anhydrides polypropylene, the acid anhydrides polyethylene, Polyurethane, polystyrene, acid anhydrides ethylene-propylene rubber(EPR), paracril; styrene-butadiene rubber(SBR) or silastic polymer or polymer blend polypropylene/polymeric amide 11; polypropylene/polymeric amide 12; polypropylene/acid anhydrides polypropylene; polyethylene/acid anhydrides polyethylene; polyamide 6/acid anhydrides polypropylene; polyamide 66/acid anhydrides polypropylene; polymeric amide 11/ acid anhydrides polypropylene; polymeric amide 12/ acid anhydrides polypropylene; polyamide 1010/acid anhydrides polypropylene or Polyurethane/acid anhydrides polypropylene; Organic modification montmonrillonite, be made up of following component: (by weight) polynite 16～40 grams, cationite are primary amine, secondary ammonium or tertiary amine 3.8～19.2 grams; Disperseing the WATER AS FLOW MEDIUM of polynite is 500～1500ml, the WATER AS FLOW MEDIUM 100～500ml of dispersible cationic exchanger; The ratio of cation modifier mole number and the ion-exchange capacity of polynite is less than 1.

2. according to claims 1 described a kind of exfoliated polymer and Nano composite material of montmorillonite, it is characterized in that described cationite is the primary amine stearylamine.

3. according to claims 1 described a kind of exfoliated polymer and Nano composite material of montmorillonite, it is characterized in that described cationite is the tertiary amine cetyl trimethylammonium bromide.

4. the preparation method of claims 1 described exfoliated polymer and Nano composite material of montmorillonite, the polymkeric substance of selection is a polyamide 6, polyamide 66, polymeric amide 11, polymeric amide 12, polyamide 1010, the acid anhydrides polypropylene, the acid anhydrides polyethylene, Polyurethane, polystyrene, acid anhydrides ethylene-propylene rubber(EPR), paracril; styrene-butadiene rubber(SBR) or silicon rubber or polymer blend polypropylene/polymeric amide 11; polypropylene/polymeric amide 12; polypropylene/acid anhydrides polypropylene; polyethylene/acid anhydrides polyethylene; polyamide 6/acid anhydrides polypropylene; polyamide 66/acid anhydrides polypropylene; polymeric amide 11/ acid anhydrides polypropylene; polymeric amide 12/ acid anhydrides polypropylene; polyamide 1010/acid anhydrides polypropylene or Polyurethane/acid anhydrides polypropylene; Organic modification montmonrillonite, be made up of following component: (by weight) polynite 16～40 grams, cationite are primary amine, secondary ammonium or tertiary amine 3.8～19.2 grams; Disperseing the WATER AS FLOW MEDIUM of polynite is 500～1500ml, the WATER AS FLOW MEDIUM 100～500ml of dispersible cationic exchanger; The ratio of cation modifier mole number and the ion-exchange capacity of polynite is less than 1, and the polynite of polymkeric substance or polymer blend and modification is 50～99 parts by weight: 1～50 part;

Preparation process is as follows:

With cation exchange capacity be 50～150meq/100g polynite by weight 16～40 the gram, stir 0.5～2h in weight part 500～1000ml deionized water high speed, form stable suspension system, the cationite of 0.2～1.0 times of polynite ion-exchange capacity is added in 100～500ml deionized water, temperature 60-90 ℃, add equimolar protonating agent hydrochloric acid or sulfuric acid again, emulsify at a high speed, form finely dispersed emulsion, and join in the suspension system of above-mentioned polynite, under high-speed stirring, mixed 10～60 minutes, precipitation, filter, vacuum-drying and pulverize organic montmorillonoid, the polynite of polymkeric substance or polymer blend and modification is 50～99 parts by weight: 1～50 part; Extrude fusion intercalation, directly obtain exfoliated polymer/Nano composite material of montmorillonite.