CN1289604C - Nylon 1010/montmorillonite nano composite material and its preparing method - Google Patents

Abstract

The present invention provides a nylon 1010/ montmorillonite nanometer composite material and a preparing method thereof. The raw material of the present invention comprises nylon 1010, montmorillonite, an intercalation ion exchanger, etc., wherein the montmorillonite is separated by suction filtration and wash after processed by the intercalation ion exchanger; then, the montmorillonite is mixed, extruded and granulated with the nylon 1010 after dried, ground and sieved; the nylon 1010/ montmorillonite nanometer composite material can be obtained or the montmorillonite is uniformly mixed with additives, such as nylon 1010 monomer, etc., after sieved, a dispersion medium is added, and the nylon 1010/ montmorillonite nanometer composite material can be obtained by polymerization. The resistance to temperature of the organic modification montmorillonite of the present invention is largely enhanced, and the combination properties of the nanometer composite material are superior.

Description

Nylon 1010/montmorillonite nanocomposite material and preparation method thereof

Technical field:

The invention relates to a nylon 1010/montmorillonite nanocomposite material and a preparation method thereof. Specifically relates to a nanocomposite material composed of nylon 1010 and montmorillonite and a preparation method thereof.

Background technique:

Nylon 1010 is a unique nylon variety in China. Castor oil, the raw material for nylon 1010, comes from castor beans. Castor is widely produced in my country, so that the production of nylon 1010 has a rich source of raw materials. Nylon 1010 can not only be used to make synthetic fibers, but also can be processed into plastic products to replace precious metals such as non-ferrous metal copper and stainless steel in engineering for the manufacture of mechanical parts. Nylon 1010 occupies a very important position in civil and national defense industries. However, nylon 1010, like other nylon products, has a large hygroscopicity, a much larger thermal expansion coefficient than metal, and poor thermal conductivity. In response to the weakness of nylon 1010, new varieties of elastomers, non-elastomeric toughened nylons, heat-resistant nylons and inorganic-filled reinforced nylons for the purpose of modification have emerged in recent years. A kind of modified nylon 1010 is also provided in the patent CN 1039825A. It is made of nylon 1010 and polyethylene with polar branches. The low temperature toughness of this modified polyamide 1010 is significantly improved, and it has better low temperature impact strength and elongation at break. However, advanced nanotechnology has irreplaceable advantages compared with conventional modification methods. In 1987, Toyota Corporation of Japan proposed the first plastic nanocomposite patent, and cooperated with Ube Industries (UBE) to develop nylon/montmorillonite nanocomposite materials. Nylon/montmorillonite nanocomposites have much better mechanical properties, thermal properties, barrier properties, anisotropy, etc. than traditional filling materials. This material has a low content of inorganic components and is much lighter in weight than traditional filler materials. In terms of processing, traditional processing methods can be used, and the finished product can also be made into fibers or films, so that nylon/montmorillonite nanocomposites have broad application prospects, and some have commercial applications. For example, Japan's Toyota Motor Corporation has used nylon 6/montmorillonite nanocomposites to manufacture automotive engine parts. Due to its high modulus and high thermal transition temperature, the product has high hardness and good thermal stability. And there is no deformation, and the weight is also reduced by 25%, so the nylon 6/montmorillonite nanocomposite is the first mass-produced organic-inorganic nanocomposite. Therefore, it is imperative to study the modification of nylon 1010 by nanotechnology. The nylon 1010/montmorillonite nanocomposite material will also greatly improve the physical and mechanical properties of nylon 1010, and continuously expand the application field of nylon 1010.

Invention content:

The object of the present invention is to provide an organic montmorillonite with high thermal decomposition temperature, a nylon 1010/montmorillonite nanocomposite material with excellent comprehensive properties and a preparation method thereof.

Technical scheme of the present invention is:

Nylon 1010/montmorillonite nanocomposite material is mainly composed of nylon 1010, montmorillonite, intercalation ion exchanger, etc., and the components are as follows in parts by weight:

Nylon 1010 or nylon 1010 monomer 80~110

Copolymerization component monomer 0～30

Montmorillonite 0.50～20

Intercalation ion exchanger 0.25～10

Initiator 0～20

Protonating agent 0～1.0

Additives 0～5

Dispersion medium 0～120

The preparation method of nylon 1010/montmorillonite nanocomposite is:

a. Mechanically stir 0.50-20 parts of montmorillonite in the presence of deionized water to form a stable suspension, heat it in a water bath to 50-90°C or at room temperature, add 0.25-10 parts of intercalation ion exchanger to carry out cation exchange reaction , suction filtration, washing the precipitate with deionized water, and removing the unreacted ion exchanger;

b. Heat, dry, grind and sieve the product obtained in a, add 100 parts of nylon 1010, mix evenly, extrude and granulate on a twin-screw extruder to obtain the product.

The preparation method of nylon 1010/montmorillonite nanocomposite material can also be:

a. Mechanically stir 0.50-20 parts of montmorillonite in the presence of deionized water to form a stable suspension, heat it in a water bath to 50-90°C or at room temperature, add 0.25-10 parts of intercalation ion exchanger to carry out cation exchange reaction , suction filtration, washing the precipitate with deionized water, and removing the unreacted ion exchanger;

b. Grind 0.5-20 parts of organomontmorillonite modified by intercalation agent and 100 parts of nylon 1010 monomer and mix evenly, add 5-30 parts of copolymerization component monomer, 0.05-5 parts of additive, 0.001-1 1 part of protonating agent and 0.01-20 parts of initiator, mixed evenly, put into a polymerization kettle, add 1-120 parts of dispersion medium, heat up to 190-240°C under the protection of carbon dioxide gas, and polymerize for 4-6 hours to obtain the product.

The advantages of the present invention are:

1, the preparation method of nylon 1010/montmorillonite nano-composite material provided by the present invention, the prepared modified organic montmorillonite interlayer spacing is relatively large, about 3～6 nanometers, this makes modified organic montmorillonite in Dispersion in the polymer resin matrix becomes easy. The fastest thermal decomposition temperature of the obtained modified organomontmorillonite is relatively high, especially the organomontmorillonite treated with polyvinylpyrrolidone or its co-treatment with organic amines, the fastest thermal decomposition temperature is 451.6 ℃ and 439.1 ℃ respectively , almost reaching the collapse temperature of montmorillonite crystals, 500°C to 600°C. This makes all kinds of organic montmorillonite applicable to the processing and molding of nylon 1010, which greatly broadens the applicable processing range of organic montmorillonite.

2. In the nylon 1010/montmorillonite nanocomposite material of the present invention, the montmorillonite dispersed phase reaches a scale of 10-50 nanometers, and has a very large interface area. The interface between the inorganic dispersed phase and the polymer matrix has ideal bonding properties, which can eliminate the mismatch of thermal expansion coefficients between the inorganic substance and the polymer matrix, and give full play to the inherent excellent mechanical properties and high heat resistance of the inorganic substance.

3. The nylon 1010/montmorillonite nanocomposite material of the present invention has greatly improved physical and mechanical properties. This improvement can be attributed to the nanoscale dispersion of montmorillonite wafers in the nylon 1010 resin matrix and the good compatibility and strong interaction with the nylon 1010 matrix.

Detailed ways:

The nylon 1010 used in the present invention is industrial grade nylon 1010, and different grades can be selected according to the application; the used nylon 1010 monomer is industrial grade nylon 1010 salt.

The montmorillonite used is a class of non-metallic layered silicate minerals. The main mineral component is layered aluminosilicate containing 85-93% montmorillonite. The thickness of the crystal layer is 1.5-2nm. The inner surface of the layer has negative charges, each negative charge occupies an area of 25-200 Ȧ ² , and the specific surface area is 700-800 m ² /g. The interlayer cations Na ⁺ , Ca ²⁺ , Mg ²⁺ , etc. are exchangeable cations. After the exchange reaction between organic ammonium and montmorillonite, the lamellar spacing can be expanded, which is beneficial for the insertion of polymer molecular chains into the montmorillonite sheets to form nanocomposites. The cation exchange capacity (CEC) of the selected montmorillonite is 50-200meq/100g, preferably 90-110meq/100g, wherein the sodium ion exchange capacity is 70-90meq/100g. When the CEC is greater than 200meq/100g, the extremely high interlayer Coulomb force makes it difficult for montmorillonite to disperse uniformly in the polymer matrix at the nanoscale; when the exchange capacity is lower than 50meq/100g, montmorillonite cannot effectively interact with the polyamide matrix Resin interaction, which is not enough to ensure the compatibility of montmorillonite and polymer matrix, also makes it difficult for montmorillonite to disperse uniformly in the polymer matrix.

The montmorillonite should be crushed to an appropriate particle size. The montmorillonite can be crushed into the desired particle size with a ball mill, vibration mill, jet mill, etc. The general particle size should be 200-400 mesh, and the thickness of the clay layer should be 9.6 Ȧ. The interlayer distance is 2-5 Ȧ, and after modification treatment, the interlayer distance of the clay is at least 20 Ȧ. The greater the distance between clay layers, the greater the improvement in mechanical properties and heat resistance.

The content of the used montmorillonite is 0.50-20 (parts by weight). When the content is less than 0.50 parts, the montmorillonite is not enough to produce sufficient reinforcement; when the content exceeds 20 parts, the montmorillonite will be agglomerated in large quantities, which will affect the performance of the material. In the present invention, the optimum content range of montmorillonite is 1-10 parts.

The intercalation ion exchangers used are organic low-molecular or high-molecular compounds such as organic amines, pyridines, phenols, alcohols, esters, amides, carboxylic acids, and acid anhydrides, among which organic amines are hexadecane Trimethyl ammonium bromide, octadecyl trimethyl ammonium chloride, dodecyl dimethyl benzyl ammonium chloride, dioctadecyl dimethyl ammonium chloride, dodecyl trimethyl ammonium One or more of ammonium chloride and ammonium bromide; pyridines are polyvinylpyrrolidone; phenols are m-cresol; alcohols are isopropanol; esters are n-butyl acetate; Methylformamide, the carboxylic acid is citric acid, and the acid anhydride is maleic anhydride. These organic low-molecular or high-molecular compounds can be used alone or in combination. Since the polymer intercalation ion exchanger has better heat resistance than the organic low molecular weight, the thermal decomposition temperature of the modified organic montmorillonite is higher, so it can be used in the processing of nylon 1010. In addition, the intercalation ion exchanger has good compatibility and interfacial bonding effect with nylon 1010 matrix resin, which is conducive to the uniform dispersion of organic montmorillonite in nylon 1010 resin, which can greatly improve the mechanical properties and Thermal properties, etc.

The copolymerization component monomer used is one of caprolactam, capryllactam, laurolactam and butyrolactam, and the above-mentioned copolymerization component monomers of industrial grade can be used.

The protonating agent used is one of phosphorous acid, phosphoric acid, hydrochloric acid, sulfuric acid, sulfonic acid, acetic acid, trichloroacetic acid, isophthalic acid or phthalic acid.

The initiator used is 6-aminocaproic acid, twelve amino acids or amino acids with 4-19 carbon atoms.

The additives used are polyamines, stabilizers, color enhancers, lubricants, toughening agents, nucleating agents and the like. Its role is to improve the toughness and stiffness of the composite material and further reduce the size of the spherulites by controlling the crystallization form and molecular structure of the resin and its intercalation with clay, so as to improve the transparency of the composite material. Polyamines include diamines, such as hexamethylenediamine, dodecyldiamine, etc.; or triamines, tetramines, pentamines, etc. The nucleating agent may be phosphate, stearate, talc, disodium phenyl phosphate and the like. Additives can be used alone or in combination.

The role of the dispersion medium used is to promote the dispersion of the clay in the polymer monomer and to improve the heat transfer mode and so on. The dispersion medium depends on the type of clay, monomer, protonating agent and initiator. A good dispersion medium should make the clay easy to disperse and have good compatibility with monomers, protonating agents and catalysts. The dispersion medium can be water, ethanol, methanol, propanol, isopropanol, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, acetic acid, fumaric acid, 1,4-butane diol, etc.

The following non-limiting examples further illustrate the embodiments and effects of the present invention.

Example 1.

Add 100 g of water to 3 g of montmorillonite with a cation exchange capacity of 100 meq/100 g, and after uniform dispersion, stir at high speed for 1 hour and age for 1 week to obtain montmorillonite suspension A.

Heat the suspension A to 70°C under the action of mechanical stirring; dissolve 1.5g of cetyltrimethylammonium bromide in 20ml of warm water, slowly add it to the suspension A, stir vigorously, and keep the constant temperature for 3 hours; After the end, suction filter and wash the product until there is no Br ^- ion in the filtrate (can be tested by AgNO ₃ solution); the filtrate is dried, ground, and passed through a 360-mesh sieve to obtain organic montmorillonite, marked as OM-01.

At room temperature, 1.5 g of polyvinylpyrrolidone was dissolved in 20 ml of deionized water, slowly added to the suspension A, vigorously stirred, and reacted for 3 hours. After the reaction, dry at low temperature, grind, and pass through a 360-mesh sieve to obtain organic montmorillonite, marked as OM-02.

Dissolve 3g of polyvinylpyrrolidone in 30ml of deionized water to form solution B. Dissolve 0.5 g of cetyltrimethylammonium bromide in 5 ml of warm water, slowly add it into suspension A, stir vigorously, and keep constant temperature for 2 hours. Then slowly add solution B, keep constant temperature, and react with high-speed stirring for 8 hours. After the reaction, dry at low temperature, grind, and pass through a 360-mesh sieve to obtain organic montmorillonite, marked as OM-03.

Slice or granulate fully dried industrial product grade nylon 1010, mix it with the above-mentioned different organic montmorillonite in a kneader according to a ratio of 100:5 (weight ratio), add liquid paraffin while stirring, and then pass through a twin-screw The extruder is extruded and granulated to obtain the nylon 1010/montmorillonite nanocomposite material.

The properties of the prepared organic montmorillonite and Na-montmorillonite (Na-Montmorillonite, MMT) were analyzed by TG, DTG and X-ray diffraction experiments, and the data are shown in Table 1.

Table 1. The various performances of embodiment 1 montmorillonite Example Thermal weight loss (%) High thermal decomposition temperature (℃) Interlayer spacing (nm) OM-01OM-02OM-03MMT 33.4336.5756.093.20 254.4, 268.0451.6439.1-- 4.203.503.711.27

The organic montmorillonite is added to the nylon 1010 matrix and dispersed evenly. Part of the nylon 1010 molecular chain can be inserted into the middle of the sheet silicate layer, and the silicate sheet layer will in turn have a major impact on the crystal structure of nylon 1010. These Structural changes will affect the mechanical properties of nylon 1010 to a certain extent. The tensile, bending and impact properties of nylon 1010 and its montmorillonite nanocomposites were tested, and the results are listed in Table 2.

It can be seen from the data in the table that the density, tensile strength and elongation at break of all the samples filled with fillers have decreased. However, the PCN-03 nanocomposite has the highest flexural strength, which is 24.2% higher than that of pure nylon 1010, and its flexural modulus is 1.6 times that of pure nylon 1010. In addition, the bending performance of PCN-04 is also greatly improved compared with pure nylon 1010. In terms of impact strength, all samples have improved except PCN-03, which is basically maintained. Among them, PCN-04 has the highest impact strength, which has increased by 6%.

The heat deflection temperature of each sample is characterized by the temperature at which the Young's modulus decays to 0.9GPa on the dynamic thermomechanical property spectrum. It can be seen that the heat distortion temperature of each sample is higher than that of pure nylon 1010, among which PCN-04 is the highest, reaching 56°C, which is 25°C higher than that of pure nylon 1010.

Table 2. The properties of nylon 1010/montmorillonite nanocomposite in embodiment 1 performance PCN-01 PCN-02 PCN-03 PCN-04 Montmorillonite type Montmorillonite content (phr) density (g/cm ³ ) tensile strength (MPa) elongation at break (%) flexural strength (MPa) flexural modulus (MPa) notched impact strength (kJ/m ² ) heat deflection temperature (°C) ----1.4370383335213.3331 OM-013.01.2255295377393.4155 OM-023.01.245462418183.3055 OM-033.01.2353154387713.5256

Example 2.

Mechanically stir 0.5-20 parts of montmorillonite in the presence of deionized water to form a stable suspension, heat it in a water bath to 50-90 ° C or at room temperature, add 0.25-10 parts of intercalated ion exchangers to carry out cation exchange reaction, pump Filter, wash the precipitate with deionized water, remove the unreacted ion exchanger, and modify the organic montmorillonite;

Grind 0.5-20 parts of the above-mentioned modified organic montmorillonite with 100 parts of nylon 1010 monomer and mix evenly, add 5-30 parts of copolymerization component monomer, 0.5-5 parts of additive, 0.001-1 part of protonating agent and 0.01 ～20 parts of initiator, mixed evenly, put into the polymerization kettle, then add 1～20 parts of dispersion medium, and raise the temperature to 190～240℃ under the protection of carbon dioxide gas to polymerize for 4～6 hours to obtain nylon 1010/montmorillonite nano composite material.

Table 3. Various properties of the nylon 1010/montmorillonite nanocomposite of embodiment 2 performance Nylon 1010/montmorillonite nanocomposite Nylon 1010 Tensile strength (MPa) Tensile modulus (MPa) Elongation at break (%) Notched impact strength (kJ/m ² ) Molecular weight (M _η ×10 ^-4 ) 48.2464.232916.91.67 37.1257.948412.02.49

The mechanical property comparison (as shown in table 3) of nylon 1010/montmorillonite nanocomposite material and nylon 1010, tensile strength has improved 30%; Young's modulus improves 80%; Elongation at break reduces to some extent; Impact strength A 41% improvement.

The above results show that when the content of montmorillonite is not high, there is a strong strengthening effect. This is mainly attributed to the nanoscale dispersion of montmorillonite wafers and their strong interfacial interactions with the matrix.

Claims (13)

1. Nylon 1010/montmorillonite nanocomposite material mainly consists of nylon 1010, montmorillonite and intercalation ion exchanger, characterized in that: each component is Nylon 1010 or nylon 1010 monomer 80～110 Copolymerization component monomer 0～30 Montmorillonite 0.50～20 Intercalation ion exchanger 0.25～10 Initiator 0～20 Protonating agent 0～1.0 Additives 0～5 Dispersion medium 0～120 2. According to claim 1, the nylon 1010/montmorillonite nanocomposite material is characterized in that: said montmorillonite is montmorillonite aluminosilicate containing 85-93%, and the particle size is 200-400 The size of the dispersed phase is 10-50 nanometers, and the cation exchange capacity is 50-200meq/100g. 3. The nylon 1010/montmorillonite nanocomposite material according to claim 1, characterized in that said nylon 1010 monomer is nylon 1010 salt. 4. The nylon 1010/montmorillonite nanocomposite material according to claim 1, characterized in that said copolymerization component monomer is one of caprolactam, capryllactam, laurolactam and butyrolactam. 5. According to claim 1, the nylon 1010/montmorillonite composite material is characterized in that: said intercalation ion exchanger is organic amines, pyridines, phenols, alcohols, esters, amides, One or more of carboxylic acid and acid anhydride organic low-molecular or high-molecular compounds. 6. The nylon 1010/montmorillonite composite material according to claim 5, wherein said organic amines are hexadecyltrimethylammonium bromide, octadecyltrimethylammonium chloride , one or more of dodecyl dimethyl benzyl ammonium chloride, dioctadecyl dimethyl ammonium chloride, dodecyl trimethyl ammonium chloride, ammonium bromide, pyridine Polyvinylpyrrolidone, m-cresol for phenols, isopropanol for alcohols, n-butyl acetate for esters, dimethylformamide for amides, citric acid for carboxylic acids, maleic anhydride for anhydrides . 7. The nylon 1010/montmorillonite nanocomposite material according to claim 1, characterized in that: said initiator is 6-aminocaproic acid or dodecanoic acid. 8. The nylon 1010/montmorillonite nanocomposite material according to claim 1, wherein said protonating agent is one of phosphorous acid, phosphoric acid, hydrochloric acid, sulfuric acid, and acetic acid. 9. The nylon 1010/montmorillonite nanocomposite material according to claim 1, wherein the additive is 1,6-hexamethylenediamine or dodecyldiamine. 10. The nylon 1010/montmorillonite nanocomposite material according to claim 1, wherein the dispersion medium is one of water, ethanol, propanol, and chloroform. 11. The method for preparing the nylon 1010/montmorillonite nanocomposite material according to claim 1, characterized in that: a. Mechanically stir 0.50-20 parts of montmorillonite in deionized water to form a stable suspension, heat it in a water bath to 50-90°C or at room temperature, add 0.25-10 parts of intercalated ion exchangers for cation exchange reaction, pump Filter, wash the precipitate with deionized water, and remove the unreacted ion exchanger; b. Heat, dry, grind and sieve the product obtained in a, add 80-110 parts of nylon 1010, mix evenly, extrude and granulate on a twin-screw extruder to obtain the product. 12. The method for preparing the nylon 1010/montmorillonite nanocomposite material according to claims 1 and 2, characterized in that: a. Mechanically stir 0.50-20 parts of montmorillonite in deionized water to form a stable suspension, heat it in a water bath to 50-90°C or at room temperature, add 0.25-10 parts of intercalated ion exchangers for cation exchange reaction, pump Filter, wash the precipitate with deionized water, and remove the unreacted ion exchanger; b. Grind 0.5-20 parts of the product obtained in a and 80-110 parts of nylon 1010 monomer and mix evenly, add 5-30 parts of copolymerization component monomer, 0.05-5 parts of additive, 0.001-1 part of protonating agent and 0.01 ～20 parts of initiator, mixed evenly, put into the polymerization kettle, add 1～120 parts of dispersion medium, raise the temperature to 190～240℃ under the protection of carbon dioxide gas and polymerize for 4～6 hours to obtain the product. 13. The preparation method of nylon 1010/montmorillonite nanocomposite according to claims 10 and 11, characterized in that the cation exchange capacity is 90-110meq/100g.