CN1284827C - Master batch of polyamide/rectorite nano composite materials and method for preparing same - Google Patents
Master batch of polyamide/rectorite nano composite materials and method for preparing same Download PDFInfo
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- CN1284827C CN1284827C CN 200410061201 CN200410061201A CN1284827C CN 1284827 C CN1284827 C CN 1284827C CN 200410061201 CN200410061201 CN 200410061201 CN 200410061201 A CN200410061201 A CN 200410061201A CN 1284827 C CN1284827 C CN 1284827C
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Abstract
The present invention relates to a mater batch of a composite nanometer polyamide / rectorite material and a preparation method thereof, which belongs to the field of composite organic macromolecule materials and is prepared by fetching 20 to 80 shares of organic rectorite by mass, 20 to 80 shares of polyamide by mass and 0.1 to 1.0 share of antioxidant by mass, and the components are melted, mixed, extruded, cooled and pelleted by a double-screw extruder. The mater batch has good compatibility with polyamide substrate resin, is favorable to the stripping and the homogeneous dispersion of the rectorite in a substrate to form the composite nanometer polyamide / rectorite material. The mater batch has the notable characteristics of enhancing the tensile strength, the bending strength and the modulus of elasticity of polymers, keeping the impact strength basically unchanged or increased, and achieving the aim of strengthening, toughness enhancement and toughness maintenance. The mater batch can also obviously increase the heat distortion temperature, the gas barrier property, the fire retardance and the ultraviolet resistance of the polymers, can be widely applied to the preparation of various composite nanometer polyamide materials, and is suitable for modifying and processing plastics, rubber and fiber. The method of the present invention has the advantages of simplicity, convenience, easy industrialized production.
Description
Technical field
The present invention relates to masterbatch of a kind of polymeric amide/rectorite nano composite material and preparation method thereof, belong to the field of organic polymer composite.
Background technology
Since institute of central authorities of Japanese Toyota in 1986 made polymeric amide/montmorillonite nano-composite material with graft process, for polyamide/laminated silicate, particularly the development of montmorillonite nano-composite material had obtained very big progress.Generally, nano composite polymer/laminated silicate material all is a layer silicate mineral synthetic of taking directly to add layered silicate or process organic modification.China Hangzhou Hongyan Electric Co., Ltd had applied for " masterbatch of a kind of high organo montmorillonite content and preparation method thereof " patent in 2003, and application number is 03137638.X, and pointed out that this masterbatch can be used for the modification of polyvinyl chloride, polypropylene and polyamide 6.But studies show that with the polymer nanocomposites of montmorillonite intercalation clay or masterbatch preparation, its weak point is in the tensile strength and flexural strength and Young's modulus thereof that improve polymkeric substance, has but seriously reduced the shock strength of polymkeric substance.
Though rectorite leng also belongs to layer silicate mineral, with montmorillonite similarity is arranged, a montmorillonite layer is all arranged, can be used for the synthetic polymer matrix material.Polymer composites generally is after utilizing clay powder, polymer base material or monomer and auxiliary agent to mix, to make through melt extruding.This technology difficulty makes clay powder homodisperse, and peels off and become nanocomposite, thereby has influenced substantially improving and improving of polymer materials performance; Simultaneously, directly adopt the clay powder, be difficult for mixing in the processing, and dust is big, contaminate environment; In addition, clay powder volume is bulk, is unfavorable for packing and transportation.In order to solve the deficiency of above-mentioned technology, best method is that powder is made masterbatch.The present invention proposes masterbatch of a kind of polymeric amide/rectorite nano composite material and preparation method thereof.At present, adopt rectorite leng, at home and abroad all be not reported as the feedstock production masterbatch.
Summary of the invention
The object of the present invention is to provide a kind of masterbatch that is used for synthesizing polyamides/rectorite nano composite material, can overcome the deficiency of above-mentioned technology, make the masterbatch of preparation in the tensile strength, flexural strength and the Young's modulus that improve polymkeric substance, keep its shock strength, can strengthen, increase just, can protect tough again; And has high cost performance, easy to use, favourable transportation, environment friendliness; Another object of the present invention provide a kind of easy and simple to handle, energy consumption is low, is easy to the preparation method of suitability for industrialized production.
Take following measures for reaching purpose of the present invention: a kind of masterbatch of polymeric amide/rectorite nano composite material is provided, it is characterized in that material composition mass fraction is: organic rectorite 20～80, polymeric amide 20～80, oxidation inhibitor 0.1～1.0.
Organic rectorite described in the masterbatch of the present invention obtains by rectorite leng being carried out organic cation exchange intercalation processing.Used rectorite leng is a kind of layered silicate that contains rectorite leng 60%～95%, and its cation exchange capacity CEC is 0.25～0.60mmol/g, the about 2.0～2.6nm of structural unit bed thickness of rectorite leng, the about 5～5000nm of width and length; This type of rectorite leng comprises calcium base rectorite leng, sodium base rectorite leng, potassium base rectorite leng, magnesium base rectorite leng, aluminium hydrogen base rectorite leng and composition thereof.
Organic rectorite described in the masterbatch of the present invention obtains by rectorite leng being carried out organic cation exchange intercalation processing, used organic cation exchanger comprises amine or amine salt, amino acid, lactan, diamine diacid salt, quaternary ammonium salt, quaternary alkylphosphonium salt and composition thereof.It is 6～22 straight chained alkyl that 1～2 carbonatoms is arranged in their molecular structures, and remaining group is that carbonatoms is 1～10 alkyl, benzyl, hydroxyl alkyl, aryl, alkylene, carboxyl or ester group.
Organic rectorite described in the masterbatch of the present invention, its preparation method is to be that 0.1%～15% rectorite leng places reactor with massfraction, add an amount of water, stir with homogenizer, rectorite leng is dispersed in becomes rectorite leng suspension in the water, add massfraction again and be 0.1%～7.5% organic cation exchanger, continue to stir 0.5～8h, become organic rectorite suspension, then after filtration or centrifugal, washing, dewater to water content be 40%～50% organic rectorite, under 60～140 ℃ temperature, be dried to the organic rectorite water content below 0.3%, be crushed to 15～74 μ m at last.
Polymeric amide described in the masterbatch of the present invention is characterized in that described polymeric amide is polyamide 6, polymeric amide 9, polyamide 66, polymeric amide 11, polymeric amide 12, polyamide 6 10, polyamide 6 12, polymeric amide 46, polyamide 1010, copolyamide 6/66, copolyamide 6/1010, copolyamide 6/66/1010 and composition thereof.
Oxidation inhibitor described in the masterbatch of the present invention is characterized in that described oxidation inhibitor forms by 1010 and 168, and its mass ratio is 3: 2.
Antioxidant 1010 described in the masterbatch of the present invention is four [(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, and oxidation inhibitor 168 is three (2, the 4-di-tert-butyl-phenyl) phosphorous acid esters.Antioxidant 1010 and 168 mass ratio are 3: 2.
The present invention also provides a kind of method for preparing the masterbatch of above-mentioned polymeric amide/rectorite nano composite material, it is characterized in that by mass fraction 20～80 organic rectorites, 20～80 polymeric amide and 0.1～1.0 oxidation inhibitor, in high-speed mixer, mixed 20～60 minutes, place on the parallel dual-screw extruding machine, barrel temperature is set at 160～280 ℃, screw speed is 100～250 rev/mins, and melting mixing is extruded, cooling, pelletizing, makes masterbatch.
In the masterbatch preparation process of the present invention, the proportioning of each material adopts mass fraction to represent.
The present invention behind the mixing, must be heated to raw material more than the base-material fusing point with mixture in twin screw extruder in high-speed mixer, extrudes behind the melting mixing, cooling, pelletizing, makes masterbatch of the present invention.
The masterbatch of the polymeric amide/rectorite nano composite material of the present invention preparation, as a kind of novel multifunctional Nano filling, compare with the masterbatch that montmorillonite or other layered silicate are made and to have following advantage:
1. the masterbatch of the present invention preparation, owing to contain organic rectorite leng, its organic rectorite is to adopt structure unique and rare layered silicate interbed mineral---rectorite leng is that raw material is made, rectorite leng is dioctahedron mica layer and 1: 1 regular interbed mineral of montmorillonite layer, compare many mica layers in different is its structural unit with montmorillonite.Between its montmorillonite layer isomorphous substitution a little less than, the interlayer negative charge is lower, helps organic intercalation and peels off, and is scattered in the polyamide substrate equably, thereby forms the nano composite material of excellent performance.
2. the masterbatch of the present invention's preparation forms typical ribbon and fibrous owing to organic rectorite disperses the back, and fiber characteristics is obvious, and length-to-diameter ratio is big.Use masterbatch of the present invention and make polymkeric substance/rectorite nano composite material, tensile strength, flexural strength and the Young's modulus of polyamide nano-composite are obviously improved, and can make the constant substantially or increase to some extent of its shock strength, both reached and strengthened, increased just, toughness reinforcing again or protect tough purpose.This is the outstanding feature of the present invention.
3. the masterbatch of the present invention's preparation has thermal property, the heat-drawn wire that can obviously improve polymkeric substance, makes heat-drawn wire improve 30%～100%, and has advantages such as good air-tightness, barrier, flame retardant resistance and anti-ultraviolet property.
4. the add-on of the masterbatch of the present invention preparation is low, and is about 4%～10%, and the cost performance height is easy to use, the environment friendliness, and favourable transportation can be widely used in preparing various polymer nanocomposites.
5. the preparation method of masterbatch of the present invention is easy and simple to handle, energy consumption is low, is easy to suitability for industrialized production.
Embodiment
Embodiment 1: containing the rectorite leng massfraction with 100 parts is that 95% rectorite leng places reactor, add 1000 parts of water, high-speed stirring 2h, become rectorite leng suspension, add 35 parts of octadecyl trimethyl ammonium chloride again, stirring reaction 6h, generate organic rectorite suspension, after filtration, after the washing, dehydration, less than 0.3%, levigately promptly obtain organic rectorite to 15～75 μ m 100 ℃ of water content that are dried to organic rectorite.Get 50 parts of prepared organic rectorite lengs, 50 parts of polyamide 6s, 0.15 part of antioxidant 1010 and 0.10 part of oxidation inhibitor 168 by mass fraction again, in high-speed mixer, mixed 30 minutes, place on the parallel dual-screw extruding machine, 220～260 ℃ of barrel temperatures are set, screw speed is 180 rev/mins, melting mixing is extruded, cooling, pelletizing, promptly makes masterbatch of the present invention.
Embodiment 2～5: operation is with example 1, and wherein the composition of organic rectorite, polymeric amide, oxidation inhibitor sees Table 1 in each example.
The composition of the different masterbatch of table 1 is pressed mass fraction
| Embodiment | 2 | 3 | 4 | 5 | |
| Organic rectorite | 80 | 60 | 30 | 20 | |
| Polyamide 6 | 20 | 40 | 70 | 80 | |
| Oxidation inhibitor | 1010 | 0.06 | 0.21 | 0.45 | 0.60 |
| 168 | 0.04 | 0.14 | 0.30 | 0.40 | |
Embodiment 6: operation is with example 1, and wherein will adding 100 parts, to contain the rectorite leng massfraction be 95% rectorite leng, and changing 100 parts of addings into, to contain the rectorite leng massfraction be 70% rectorite leng.
Embodiment 7: operation wherein will add 35 parts of octadecyl trimethyl ammonium chloride with example 3, change into adding 38 parts of hexadecyl triphenyl bromide phosphines.
Embodiment 8: operation wherein will add 35 parts of octadecyl trimethyl ammonium chloride with example 3, change into adding 40 parts of distearyl dimethyl ammonium chlorides.
Embodiment 9: operation wherein will add 40 parts of polyamide 6s and change 40 parts of polyamide 66s of adding into example 7, barrel temperature is set change 240～280 ℃ at 220～260 ℃.
Embodiment 10: operation wherein will add 40 parts of polyamide 6s and change 40 parts of polyamide 6s 10 of adding into example 7, barrel temperature is set change 230～280 ℃ at 220～260 ℃.
Embodiment 11: operation wherein will add 40 parts of polyamide 6s and change 40 parts of copolyamides 6/66 of adding into example 8, temperature is set change 160～220 ℃ at 220～260 ℃.
Embodiment 12: operation wherein will add 40 parts of copolyamides 6/66 and change 40 parts of copolyamides 6/66/1010 of adding into example 11.
Embodiment 13: operation wherein will add 40 parts of copolyamides 6/66 and change 40 parts of copolyamides 6/1010 of adding into example 11, temperature is set change 190～240 ℃ at 160～220 ℃.
Embodiment 14: operation wherein will add 70 parts of polyamide 6s and change 50 parts of polyamide 6s of adding and 20 polymeric amide 9 into example 4.
The masterbatch of polymeric amide/rectorite nano composite material of the present invention can be widely used in preparing various polymer nanocomposites, is suitable for the modification and the processing of plastics, rubber and fiber.
Claims (3)
1. the masterbatch of a polymeric amide/rectorite nano composite material is characterized in that material composition mass fraction is: organic rectorite 20～80, polymeric amide 20～80, oxidation inhibitor 0.1～1.0.
2. masterbatch according to claim 1 is characterized in that described polymeric amide is polyamide 6, polymeric amide 9, polyamide 66, polymeric amide 11, polymeric amide 12, polyamide 6 10, polyamide 6 12, polymeric amide 46, polyamide 1010, copolyamide 6/66, copolyamide 6/1010, copolyamide 6/66/1010 or its mixture.
3. method for preparing the masterbatch of the described polymeric amide/rectorite nano composite material of claim 1: get organic rectorite 20～80 by mass fraction, polymeric amide 20～80, oxidation inhibitor 0.1～1.0, in high-speed mixer, mixed 20～60 minutes, place on the parallel dual-screw extruding machine, barrel temperature is set at 160～280 ℃, screw speed is 100～250 rev/mins, melting mixing is extruded, cooling, pelletizing, makes masterbatch.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 200410061201 CN1284827C (en) | 2004-11-29 | 2004-11-29 | Master batch of polyamide/rectorite nano composite materials and method for preparing same |
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| CN 200410061201 CN1284827C (en) | 2004-11-29 | 2004-11-29 | Master batch of polyamide/rectorite nano composite materials and method for preparing same |
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| CN1631977A CN1631977A (en) | 2005-06-29 |
| CN1284827C true CN1284827C (en) | 2006-11-15 |
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| CN102120880A (en) * | 2011-02-24 | 2011-07-13 | 西北工业大学 | High-strength organic rectorite/nylon nano composite material and preparation method thereof |
| CN111518369A (en) * | 2020-05-21 | 2020-08-11 | 成都玉龙化工有限公司 | Flame retardant and preparation method thereof |
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