CN101205361A - Montmorillonite layered nylon6/montmorillonite nano composite material and preparation thereof - Google Patents
Montmorillonite layered nylon6/montmorillonite nano composite material and preparation thereof Download PDFInfo
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- CN101205361A CN101205361A CNA2007101713222A CN200710171322A CN101205361A CN 101205361 A CN101205361 A CN 101205361A CN A2007101713222 A CNA2007101713222 A CN A2007101713222A CN 200710171322 A CN200710171322 A CN 200710171322A CN 101205361 A CN101205361 A CN 101205361A
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Abstract
The invention relates to a nanocomposite of nylon 6/ montmorillonite in the shape of a montmorillonite laminiplantation and a preparation method thereof. The nanocomposite is made up of 100 shares of nylon 6, 1 to 10 shares of modified montmorillonite and 0.1 to 1 share of antioxidizer; the nanocomposite is a stripping material obtained by melting intercalation. The nylon 6/ montmorillonite nanocomposite with special micro morphostructure is manufactured sequentially by realizing melting intercalation by means of twin-screw extrusion, by injection premolding, and by exerting high pressure from a flat vulcanizing machine with a temperature ranging between 20 DEG C and 100 DEG C thus producing solid flow. The montmorillonite, dispersing in polymeric matrix of the nanocomposite, is in a high parallel alignment. The nanocomposite is internally provided with micro laminated structure similar with the internal structure of seashell, and has larger elongation fracture tensile rate than common material of the same components. This is the first time to introduce bionics in macromolecule/ montmorillonite nanocomposite.
Description
Technical field
The invention belongs to the nylon composite materials field, particularly relate to stratiform nylon 6/ Nanometer Composite Material Of Montmorillonite And Its Preparation Method that a kind of polynite is arranged in parallel.
Background technology
So far, the research in existing 20 years of polymer/Nano composite material of montmorillonite is historical.Because the nanoscale effect of polynite and very strong organic-inorganic interface binding power, this type of matrix material embodies very big advantage at aspects such as intensity, thermotolerance, barriers.In these years, the fundamental research of this type of material and commercial exploitation application development are very swift and violent, and a lot of materials have been realized industrialization and commercialization.Especially nylon 6 (a kind of polymeric amide)/Nano composite material of montmorillonite is as occurring the earliest and realizing causing that people study interest greatly by industrialized polymer/Nano composite material of montmorillonite the earliest.
Chinese patent publication number CN1138593A has reported a kind of intercalation polymeric " single stage method " preparation polyamide/montmorillonite nano composite material method.Chinese patent application numbers 97112237.7 has been reported the method that will prepare nanometer composite polyamide-clay material through clay and polymeric amide melt blending basis on twin screw extruder of intercalation processing.Chinese patent publication number CN1163288A, application number 97104055.9,97112237.7 and newspapers such as 97104194.6 have reported that the method that in-situ inserted polymerization is equipped with polymer/Nano composite material of montmorillonite overcomes dispersion and the interface problem of polynite in polymkeric substance.
Yet, about the research of this class material only concentrate on by imvite modified (as finishing), intercalator select and the exploration of intercalation technology improves that peeling off of polynite disperseed and and polymeric matrix between interaction, do not relate to stratiform nylon 6/ Nano composite material of montmorillonite that the preparation polynite highly is arranged in parallel.
Summary of the invention
Stratiform nylon 6/ Nanometer Composite Material Of Montmorillonite And Its Preparation Method that the object of the present invention is to provide a kind of polynite to be arranged in parallel prepares nylon 6/ Nano composite material of montmorillonite of certain component concentration and one-step forming at the beginning of injection moulding machine by fusion intercalation; Provide bigger uniaxial tension by vulcanizing press, material is forced to flow with solid-state form in the mould of restricted boundary, and material internal forms the microcosmic lamella packing structure that is similar to shell inside because pars amorpha and crystalline region biphase texture are reset; Simultaneously, the polynite that is dispersed in the pars amorpha is shifted along with solid-state the flowing of material, and after having experienced rotation that extraneous high pressure causes and the mobile displacement that causes of polymer matrix, these inorganic sheet zones are arranged parallel to each other.This brand-new interior microscopic form and structure make this material have bigger tension fracture elongation rate.
Stratiform nylon 6/ Nano composite material of montmorillonite that a kind of polynite of the present invention is arranged in parallel, its component and content (weight part) are 6,1～10 part of modified montmorillonoid of 100 parts of nylon and 0.1～1 part of oxidation inhibitor, by the release liner of fusion intercalation acquisition.
Described nylon 6 is the technical grade nylon product, and modified montmorillonoid is the high purity polynite through the ion exchange treatment that organises, radius-thickness ratio 200,
The described ion that organises is that the organic long-chain alkylammonium salt exchanges the aquation inorganic cation in the polynite; Polynite content 96～98%, oxidation inhibitor are 1010 (four (β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol esters).
In stratiform nylon 6/ Nano composite material of montmorillonite that polynite of the present invention is arranged in parallel, the polynite that is scattered in polymeric matrix presents the arrangement mode that is parallel to each other, and can observe its low temperature ultrathin section(ing) by transmission electron microscope (TEM); Its interior microscopic form has the laminated structure feature on the micro-meter scale, and is closely similar with the microtexture of shell, can be undertaken observing behind the metal spraying by the section of scanning electronic microscope (SEM) to its brittle failure in liquid nitrogen.
Material of the present invention has very big elongation at break, and nylon 6/ Nano composite material of montmorillonite of comparing common fusion intercalation preparation improves a lot, and polynite content is many more in the material, and the degree that elongation at break improves is big more.
The preparation method of stratiform nylon 6/ Nano composite material of montmorillonite that polynite of the present invention is arranged in parallel comprises the following steps:
(1) with 100 parts of exsiccant nylon 6 pellets, 1～10 part of modified montmorillonoid and oxidation inhibitor four (β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester mixes for 0.1～1 part, through twice melt blending of twin screw extruder, granulation, four sections temperature are provided with 125～255 ℃ of scopes; Use cylinder baking oven (70～110 ℃) vacuum-drying 5～10 hours, obtain nylon 6/ Nano composite material of montmorillonite of fusion intercalation;
(2) be the uniform sheet material of thickness through injection moulding machine machine-shaping, the injection moulding machine temperature out is 230～240 ℃, and die temperature is 10～50 ℃, and melten gel pressure is 50.0～120.0bar;
(3) batten of injection moulding is put into particular mold, use vulcanizing press that it is applied uniaxial tension, batten is bilateral limited in mould, solid-state flow (plastic deformation) only takes place along its length, the homo(io)thermism of mould and material, can be 20～100 ℃ of interval selection (fluctuating range be no more than 5 ℃), pressure is 300～1500MPa, the dwell time is 3～20 minutes;
(4) after pressurize finished, finished product was taken out in the demoulding.
Beneficial effect of the present invention:
Material of the present invention has embodied a kind of brand-new arrangement mode of polynite in polymer matrix, and a kind of interior microscopic morphological structure of brand-new nylon 6/ Nano composite material of montmorillonite, this morphological structure and natural shell internal microstructure are closely similar, so can think, this is to introduce bionic thought for the first time in polymer/Nano composite material of montmorillonite research.Unique texture is given the same type of material bigger tension fracture elongation rate of material than the usual way preparation in this heterogeneous system, and its preparation method is very simple, cost is low, the possibility that is applied to produce in batches is arranged, and prospect is considerable.
Description of drawings
Fig. 1 is the low temperature ultrathin section(ing) photo that observed polynite is arranged parallel to each other under transmission electron microscope (photo is chosen the optional position, and the sections observation face is parallel to the direction that vulcanizing press is exerted pressure) of material of the present invention;
Fig. 2 is the photo of low temperature ultrathin section(ing) under transmission electron microscope of nylon 6/ Nano composite material of montmorillonite of common fusion intercalation preparation, the polynite random arrangement;
Fig. 3 is the electron scanning micrograph (photo is chosen the optional position, and section is parallel to the direction that vulcanizing press is exerted pressure) of material liquid nitrogen brittle failure section of the present invention, embodies the microcosmic laminate structure of material internal;
Fig. 4 is the electron scanning micrograph of the nylon 6/ Nano composite material of montmorillonite liquid nitrogen brittle failure section of common fusion intercalation preparation, presents random breaking morphology;
Fig. 5 is the nylon 6/ Nano composite material of montmorillonite TEM photo (low temperature ultrathin section(ing)) of montmorillonoid-containing 3%;
Fig. 6 is the nylon 6/ Nano composite material of montmorillonite SEM photo (liquid nitrogen brittle failure section) of montmorillonoid-containing 3%;
Fig. 7 is the nylon 6/ Nano composite material of montmorillonite TEM photo (low temperature ultrathin section(ing)) of montmorillonoid-containing 5%;
Fig. 8 is the nylon 6/ Nano composite material of montmorillonite SEM photo (liquid nitrogen brittle failure section) of montmorillonoid-containing 5%.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
With exsiccant 1000g nylon 6,30g modified montmorillonoid, the pre-blend of 2g antioxidant 1010, twice melt blending, granulation on the twin screw extruder of 125～255 ℃ of four sections temperature ranges obtain polynite content and are 3% intercalated nano-composite.Constant temperature vacuum-drying 7 hours in 110 ℃ cylinder baking oven is through injection moulding machine processing (230 ℃ of temperature outs, 20 ℃ of die temperatures, melten gel pressure 60.0bar) after, the premolding batten is put into the rectangular mould of being with piston, 80 ℃ of constant temperature, apply pressure 650Mpa with vulcanizing press, pressurize 5 minutes.Sample is taken out in the demoulding, promptly gets to have special micromorphologic nylon 6/ Nano composite material of montmorillonite.The tension fracture elongation rate of this material is 131%; Its low temperature ultrathin section(ing) can be observed polynite be arranged parallel to each other (Fig. 5) under transmission electron microscope; Liquid nitrogen brittle failure section can clearly be observed the microtexture (Fig. 6) that uniform sheet is piled up under scanning electronic microscope, every layer thickness is about 5um.
Embodiment 2
With 1500g nylon 6,75g modified montmorillonoid, the pre-blend of 3g antioxidant 1010,, get the nano composite material of montmorillonoid-containing 5% through twice melt blending granulation of twin screw extruder.Constant temperature vacuum-drying 6 hours in 100 ℃ cylinder baking oven is through injection moulding machine processing (230 ℃ of temperature outs, 40 ℃ of die temperatures, melten gel pressure 80.0bar) after, the premolding batten is put into the rectangular mould of being with piston, 40 ℃ of constant temperature, apply pressure 800Mpa with vulcanizing press, pressurize 10 minutes.Sample is taken out in the demoulding, obtains having special micromorphologic nylon 6/ Nano composite material of montmorillonite.The tension fracture elongation rate of this material is 176%; Its low temperature ultrathin section(ing) can be observed polynite be arranged parallel to each other (Fig. 7) under transmission electron microscope; Liquid nitrogen brittle failure section observed microscopic pattern under scanning electronic microscope is arranged in the form of sheets, interface layer clear (Fig. 8).
Claims (5)
1. stratiform nylon 6/ Nano composite material of montmorillonite that polynite is arranged in parallel, it is characterized in that: the component of this material and weight part content are 6,1～10 part of modified montmorillonoid of 100 parts of nylon and 0.1～1 part of oxidation inhibitor four (β-(3, the 5-di-tert-butyl-hydroxy phenyl) pentaerythritol ester propionic acid) is by the release liner of fusion intercalation acquisition.
2. stratiform nylon 6/ Nano composite material of montmorillonite that polynite according to claim 1 is arranged in parallel, it is characterized in that: described modified montmorillonoid is the high purity polynite through the ion exchange treatment that organises, its radius-thickness ratio 200, polynite content 96～98%.
3. stratiform nylon 6/ Nano composite material of montmorillonite that polynite according to claim 2 is arranged in parallel is characterized in that: the described ion that organises is the organic long-chain alkylammonium salt.
4. stratiform nylon 6/ Nano composite material of montmorillonite that polynite according to claim 1 and 2 is arranged in parallel, it is characterized in that: the polynite in the described material is arranged in parallel, and material internal has the laminated structure on the micro-meter scale.
5. the preparation method of stratiform nylon 6/ Nano composite material of montmorillonite that is arranged in parallel of polynite comprises the following steps:
(1) with 100 parts of exsiccant nylon 6 pellets, 1～10 part of modified montmorillonoid and oxidation inhibitor four (β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester mixes for 0.1～1 part, through twice melt blending of twin screw extruder, granulation, four sections temperature are provided with 125～255 ℃ of scopes; Use 70～110 ℃ of vacuum-dryings of cylinder baking oven 5～10 hours, obtain nylon 6/ Nano composite material of montmorillonite of fusion intercalation;
(2) be the uniform sheet material of thickness through injection moulding machine machine-shaping, the injection moulding machine temperature out is 230～240 ℃, and die temperature is 10～50 ℃, and melten gel pressure is 50.0～120.0bar;
(3) batten of injection moulding is put into mould, use vulcanizing press that it is applied uniaxial tension, batten is bilateral limited in mould, the deformation of solid flow dynamic-plasticity only takes place along its length, 20～100 ℃ of the temperature of mould and material, pressure is 300～1500MPa, and the dwell time is 3～20 minutes;
(4) after pressurize finished, finished product was taken out in the demoulding.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN2007101713222A CN101205361B (en) | 2007-11-29 | 2007-11-29 | Montmorillonite layered nylon6/montmorillonite nano composite material and preparation thereof |
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| CN2007101713222A CN101205361B (en) | 2007-11-29 | 2007-11-29 | Montmorillonite layered nylon6/montmorillonite nano composite material and preparation thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102189618A (en) * | 2010-03-16 | 2011-09-21 | 中原工学院 | Method for increasing mechanical property of PA66 by forced solid flow |
| CN104359803A (en) * | 2014-11-14 | 2015-02-18 | 河南理工大学 | Sheet-shaped powder radius-thickness ratio testing method based on scanning electron microscope |
| CN104672755A (en) * | 2015-02-05 | 2015-06-03 | 中国科学院福建物质结构研究所 | Nano composite material for melt deposition type 3D printers and preparation method thereof |
| CN106167555A (en) * | 2016-04-28 | 2016-11-30 | 华南理工大学 | A kind of imitative shell environmental protection composite membrane of interpenetrating type petal design and preparation method thereof |
| CN107177199A (en) * | 2017-05-24 | 2017-09-19 | 盐城神力制绳有限公司 | A kind of preparation method of modified organo montmorillonite/nylon 6 composite material |
| CN113881076A (en) * | 2021-11-02 | 2022-01-04 | 南京聚隆科技股份有限公司 | High-temperature-aging-resistant glass fiber reinforced nylon material and preparation method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1359979A (en) * | 2001-12-28 | 2002-07-24 | 东华大学 | Process for preparing nylon 6/montmorillonite composite |
| CN100386384C (en) * | 2003-09-03 | 2008-05-07 | 中国科学院长春应用化学研究所 | Detaching type polymer/montmorillonite composite material and preparing method thereof |
| CN100547035C (en) * | 2005-12-12 | 2009-10-07 | 上海杰事杰新材料股份有限公司 | A kind of preparation method of peel montmorillonite/casting nylon nano-composite material |
| CN100417691C (en) * | 2006-11-09 | 2008-09-10 | 四川大学 | Preparation method of nylon/montmorillonoid fire retarding composite material |
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2007
- 2007-11-29 CN CN2007101713222A patent/CN101205361B/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102189618A (en) * | 2010-03-16 | 2011-09-21 | 中原工学院 | Method for increasing mechanical property of PA66 by forced solid flow |
| CN104359803A (en) * | 2014-11-14 | 2015-02-18 | 河南理工大学 | Sheet-shaped powder radius-thickness ratio testing method based on scanning electron microscope |
| CN104672755A (en) * | 2015-02-05 | 2015-06-03 | 中国科学院福建物质结构研究所 | Nano composite material for melt deposition type 3D printers and preparation method thereof |
| CN106167555A (en) * | 2016-04-28 | 2016-11-30 | 华南理工大学 | A kind of imitative shell environmental protection composite membrane of interpenetrating type petal design and preparation method thereof |
| CN107177199A (en) * | 2017-05-24 | 2017-09-19 | 盐城神力制绳有限公司 | A kind of preparation method of modified organo montmorillonite/nylon 6 composite material |
| CN113881076A (en) * | 2021-11-02 | 2022-01-04 | 南京聚隆科技股份有限公司 | High-temperature-aging-resistant glass fiber reinforced nylon material and preparation method thereof |
| CN113881076B (en) * | 2021-11-02 | 2023-10-27 | 南京聚隆科技股份有限公司 | High-temperature aging resistant glass fiber reinforced nylon material and preparation method thereof |
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Assignee: Zhejiang Pegent Chemical Co., Ltd. Assignor: Donghua University Contract record no.: 2011330001486 Denomination of invention: Montmorillonite layer nylon 6/ montmorillonite nano composite material and preparation method thereof Granted publication date: 20100609 License type: Exclusive License Open date: 20080625 Record date: 20111228 |
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