CN1192060C - Process for preparing nano-class polyamide/laminated silicate composition - Google Patents
Process for preparing nano-class polyamide/laminated silicate composition Download PDFInfo
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- CN1192060C CN1192060C CNB011202858A CN01120285A CN1192060C CN 1192060 C CN1192060 C CN 1192060C CN B011202858 A CNB011202858 A CN B011202858A CN 01120285 A CN01120285 A CN 01120285A CN 1192060 C CN1192060 C CN 1192060C
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Abstract
The present invention provides a method for preparing a composite polyamide / layer silicate nanometer material. A melt intercalation method is adopted, and parent organic environment affinity provided by a functional co-intercalation organified layer silicate material and functional base groups capable of reacting with amido groups or amino groups are utilized; thus, the layer silicate material is combined with a polyamide substrate and uniformly dispersed in the polyamide substrate in a nanometer scale so as to prepare the composite polyamide / layer silicate nanometer material with high performance. The present invention has the advantages of simple preparation method, high productive efficiency, low cost and no environmental pollution; the obtained composite nanometer material has excellent performance.
Description
The present invention relates to a kind of method for preparing polyamide nano-composite, specially refer to and adopt melt intercalated method, utilize the functional intercalation altogether layered silicate material that organises to combine with polyamide substrate and be dispersed in the polyamide substrate, thereby prepare high performance polyamide nano-composite with nanoscale.
1. background of invention
The present invention relates to a kind of polyamide nano-composite, specially refer to the matrix material that polymeric amide and mineral filler are formed.Polymeric amide is a kind of widely used engineering plastics, is widely used in aspects such as automobile component, electrical part, fiber and packaging film.But owing to the existence of polarity amide group, cause the water-intake rate height of polymeric amide, make its dimensional stability deterioration.Its heat-drawn wire is lower, causes the mechanical and physical performance deterioration, has limited application.In addition, even under drying conditions, the mechanical and physical performance of polymeric amide is also inadequate slightly, and deficiency is used under heavy lift.Early stage method of modifying is to adopt the Inorganic Fillers Filled polymeric amide, for example, with glass-fibre reinforced polyamide 6, can improve its intensity, rigidity and dimensional stability, but the density of material is increased.Add mineral fillers such as lime carbonate or mica in addition in addition, can reduce polyamide 6 cost, improve dimensional stability and improve rigidity, but cause the strength of materials particularly impelling strength descend.An approach that improves performance is to adopt superfine mineral compound filled polymer composite.But when packing material size size during less than 0.1 micron, the great surface energy of particle makes that interparticle self aggregation effect is very big, adopts traditional blend method, can not offset the self aggregation effect, can not make filler obtain homodisperse on the nanometer level; On the other hand, for improving the bonding interface of filler and polymkeric substance, common employing silane coupling agent or titante coupling agent or other have the interfacial compatibilizers such as organic polymer grafts to the similar group of matrix macromolecular chain, to improve the consistency of filler in polymeric matrix.Yet it is very big that the chemical structure of filler and polymkeric substance and physical condition differ, and existing interface modification technology is difficult to eliminate fully the interfacial tension between filler and polymeric matrix, homodisperse of realizing ideal and bonding interface.Therefore, differ greatly apart from the INTERFACE DESIGN of molecular scale, matrix material does not reach the molecular dispersion level, and only belongs to class microcosmic matrix material, has influenced the improvement of reinforcing effect and resistance toheat.
A kind of novel method of Chu Xianing is to utilize layered silicate to prepare polymer nanocomposites in recent years.As everyone knows, polynite such as sodium-based montmorillonite or the calcium-base montmorillonite mineral of layered silicate-for example, can be by organic cation ammonium salt intercalation in dispersion medium such as water, organic molecule is introduced between the silicate lamella of nanoscale, hydrophilic silicate lamella organises thereby increased sheet interlayer spacing and made originally, and organism or high molecular polymer are had good consistency.Or/and under the effect of shearing force, when organic polymer inserts between the silicate lamella, further increase interlamellar spacing in heat, the silicate granules with 30-200 silicate lamella composition is dissociated, promptly silicate is dispersed in the polymeric matrix with single lamella.The basic thickness of silicate lamella is 0.96 nanometer, and the definition of nano material is to have unidimensional scale in the material at least less than 100 nanometers, and apparent, dissociative type layered silicate/polymer composites is a nano composite material.In layered silicate/polymer nanocomposites, polymer molecular chain and silicate lamella are at nanoscale-be compound on the molecular scale, and this will greatly promote the performance of polymer materials.
United States Patent (USP) 4,739,007 has reported the method for preparing polyamide/montmorillonite (polynite-a kind of natural layer silicate mineral) nano composite material by polymerization.The implementation process of this patent is at first the intercalation expansionization processing-processing that promptly organises to be carried out in polynite, then the common polymerization acquisition nano composite material in reactor with organo montmorillonite and monomer of polyamide.The similar United States Patent (USP) 4,810,734 in addition that utilizes the intercalation polymeric method.The mechanical property and the thermal characteristics of the nano composite material that obtains are improved.The shortcoming of above-mentioned patent is that carrying out intercalation polymeric in reactor needs main equipment, and expends a large amount of time and energy, causes production cost rising, production efficiency to descend.
Melt intercalated method prepares nano composite material can enhance productivity, and reduces production costs, and does not need special reaction equipment, is a kind of novel method that occurs in recent years.World patent WO93/04117 for example utilizes the organic cation ammonium salt to the layered silicate processing that organises, and with the silicate after organising and polyamide polymer extruding pelletization on forcing machine jointly, obtains nano composite material.Similar patent also has United States Patent (USP) 5,385,776.But in the above patent, no matter be to adopt intercalation polymeric method or melt intercalated method, what all use is the organic intercalation agent of no functional group, just utilizes electrostatic force or Van der Waals force that silicate lamella and polymeric amide molecular chain are linked together.And in fact have only when mineral filler and polymeric matrix the chemical bonding of strong interaction-is for example arranged, and reach the dispersion of nanoscale, just may be with the rigidity of inorganics, toughness, the workability of dimensional stability and thermotolerance and polymkeric substance ideally combine, the Organic of obtained performance excellence.
In order to overcome the shortcoming in the prior art, the invention provides a kind of method of utilizing melt intercalated method to prepare nano-class polyamide/laminated silicate composition with excellent mechanical property.The layered silicate that adopts has the characteristics of close organic property and reactable simultaneously through processings that organise of intercalation altogether, makes polymeric amide molecular chain and sheet interlayer generation chemical bonding.
2. main points of the present invention
Melt intercalated method is jointly at forcing machine or similarly shearing force can be provided and polymeric amide is heated to equipment more than the fusing point with polymeric amide and layered silicate material, under the effect of shearing force, make the polymeric amide molecular chain be inserted into layered silicate material sheet interlayer, making polymeric amide molecular chain and lamella is to carry out compoundly on the molecular scale in nanometer, obtains high molecular polymer/laminated nm-silicate composite material.Wherein the inorganic silicate component provides excellent mechanics, thermostability to reach water and micromolecular iris action, and organic polymer has guaranteed good workability.The present invention adopts melt intercalated method to prepare nano-class polyamide/laminated silicate composition, has made full use of the scorification simple equipments, advantages such as technology is simple, production efficiency is high, environmentally safe.Adopt simultaneously and more effectively be total to intercalation organosilicate stratified material, this material is to carry out modification on the basis of inorganic silicate stratified material, utilize organic quaternary ammonium salt and epoxy compounds to carry out common intercalation processing, layered silicate material is organised, strengthen with the organic macromolecule consistency making the polymeric amide molecular chain be easy to enter the sheet interlayer; Simultaneously can and polyamide skeleton on amide group or the epoxy compounds of amido reaction insert between the silicate lamella, exothermic heat of reaction under melting condition between functional group can make the intercalation dispersion effect better, and polyamide chains is connected on the silicate lamella securely, further improves the performance of product.The nano composite material that obtains has following characteristics: excellent oxygen and water vapour barrier property, agent of low hygroscopicity, high strength and rigidity, high heat resistance, high transparent, grease resistance, resistance to chemical attack and high-dimensional stability.
3. to the method involved in the present invention and the detailed description of material
The present invention relates to the organise preparation of layered silicate material and corresponding polyamide nano-composite of functional altogether intercalation.The functional altogether intercalation that the present invention relates to layered silicate material that organises is to organise to handle and obtain by inorganic laminated silicate material being carried out common intercalation.The inorganic laminated silicate material that the present invention relates to is meant the material with sheet crystalline structure, single lamellar spacing is between 0.5 nanometer to 2 nanometer, lamella length and width are between 10 nanometer to 1000 nanometers, and lamella and lamella rely on Intermolecular Forces or electrostatic force to pile up.This type of material comprises sodium-based montmorillonite (sodiummontmorillonite), calcium-base montmorillonite (calcium montmorillonite), magnesium base montmorillonite polynite classes (smectite) such as (magnesium montmorillonite), nontronite (nontronite), beidellite (beidelite), rich volchonskoite (volkonskoite), hectorite (hectorite), saponite (saponite), sauconite (sauconite), stevensite (stevensite), bentonite (bentonite), illite (illite), kaolin (kaolin), polynite and illitic mixture are as the tired stone (rectorite) etc. that takes off.Except above natural mineral, artificial hydro-thermal synthetic polynite and saponite are also included among the inorganic laminated silicate material of indication of the present invention.Be applicable to that best materials of the present invention is the polynite class, its single lamellar spacing is about 1 nanometer.Its unit cell is formed by carrying the layer of aluminum oxygen octahedra secretly in the middle of the two-layer silicon-oxy tetrahedron, connects by shared Sauerstoffatom between the two, and structure cell continuous growth on length and width constitutes single lamella.Because the isomorphous substitution phenomenon, the montmorillonite layer surface has negative charge, is present in the Na between the lamella
+, Ca
2+, Mg
2+Play the balancing charge effect etc. the interchangeability positively charged ion, utilize the organic cation ammonium salt can be Na
+, Ca
2+, Mg
2+Deng exchanging, thereby sheet surfaces is organised.Polynite preferably is crushed to suitable particle diameter before using, and available ball mill, vibration mill, jet mill etc. are broken into desirable particle size to clay powder, and general particle diameter should be at 200 orders-400 order.
The organic cation ammonium salt that the present invention relates to has following structure: NH
3 +R
1Or NH
2 +R
2R
3Or NH
+R
4R
5R
6Or N
+R
7R
8R
9R
10R wherein
1To R
10Being organo-functional group, can be aromatic base or alkyl, can be the same or different to each other.Be suitable for most organic cation ammonium salt of the present invention and have the 4th kind of structure, i.e. N
+R
7R
8R
9R
10, as cetyl trimethylammonium bromide.Utilize the ion exchange reaction organic cation ammonium salt can be with Na
+, Ca
2+, Mg
2+Deng exchanging, thereby with R
1To R
10Insert between the inorganic sheet Deng organo-functional group, sheet interlayer spacing is increased, and the sheet surfaces parent is organised.
The epoxy compounds that the present invention relates to comprises organic monomer, oligopolymer and superpolymer, contains an epoxide group on its molecular chain at least.Being suitable for most epoxy compounds of the present invention is the Resins, epoxy that has two epoxide groups on the molecular chain at least.
The polymeric amide that the present invention relates to comprises polyamide 6, polyamide 6,6, polymeric amide 11, polymeric amide 12, polymeric amide 4,6 and polymeric amide 10.
The functional altogether intercalation that the present invention relates to layered silicate material that organises is to carry out modification on the basis of inorganic silicate stratified material, utilizes organic cation ammonium salt and epoxy compounds to carry out common intercalation processing.Its method for making is as follows: with the inorganic silicic acid salt material of 0.1-30 part, the water high speed stirring 1-1000 part forms stable suspension earlier; Then the organic cation ammonium salt of 0.1-50 part is joined and continue in the suspension to stir, utilize ion exchange reaction to make ammonium salt insert the silicate plate interlayer and the silicate plate laminar surface is organised; After treating that permutoid reaction is finished, leave standstill silicate material is fully precipitated, remove supernatant liquid and obtain mud shape mixture, the epoxy compounds of 0.1-50 part is joined continue in the mud shape mixture fully to stir then; At last it is dehydrated and product is crushed to 200-400 order particle diameter, this final product is the functional intercalation altogether silicate material that organises.
The preparation method of the nano composite material that the present invention relates to is as follows: can provide simultaneously shearing force and and polymeric amide is heated in the equipment more than the fusing point, as twin screw extruder, with the functional altogether intercalation of 0.1-30 part organise silicate material and 100 parts of molten polyamide extruding pelletizations, can obtain nano-class polyamide/laminated silicate composition.The functional altogether intercalation silicate material content in the present invention that organises is 0.1-30 (weight part).When content is lower than 0.1 part, silicate material is not enough to produce enough enhancements; When content surpasses 30 parts, nano composite material can not machine-shaping.In the present invention, its optimum content scope is 0.5-20 part.
Method provided by the invention adopts melt intercalated method to prepare nano-class polyamide/laminated silicate composition, and simple equipments, technology is simple, production efficiency is high, environmentally safe.Adopt simultaneously more effectively to be total to intercalation organosilicate stratified material, can make the intercalation dispersion effect better, and polyamide chains is connected on the silicate lamella securely, further improve the performance of product, prepare high performance nano composite material.
The present invention makes the layered silicate material disperse phase reach the 10-30 nanoscale, has very large interfacial area, chemical bonding makes inorganic disperse phase and polymer-based carbon body interface have the ideal adhesiveproperties, inorganics and polymeric matrix two material thermal expansivity mismatch problems be can eliminate, the excellent mechanical property of inorganics intrinsic, high heat resistance, barrier given full play to.This nano composite material can have choice widely to polytype forming process.
Nanoscale dispersive silicate lamella has the heterogeneous nucleation effect to polymeric amide among the present invention, and crystallization velocity is significantly improved, and the strong interaction of sheet surfaces and polymer molecule interchain has the polymeric amide of promotion γ crystal formation nucleus formation.
Embodiment 1
With 100 parts sodium-based montmorillonite, stirred 2 hours earlier, form the stable suspersion system 1000 parts water high speeds.Then 30 parts cetyl trimethylammonium bromide is joined and continue in the suspension to stir 2 hours.After treating that ion exchange reaction is finished, leave standstill and suspension was fully precipitated in 24 hours, remove supernatant liquid and obtain mud shape mixture, (CIBA-GEIGY company makes with 40 parts of bisphenol A type epoxy resin ARALDITE GY240 then, molecular weight 340-380, oxirane value 0.52-0.56) join in the mud shape mixture and fully stirred 2 hours.At last it is dehydrated and product is crushed to 200-400 order particle diameter, promptly obtain functional intercalation organic montmorillonoid altogether.On the twin screw extruder of 30 mm dias, (the polyamide 6 trade mark is ULTRAMID B3 with 1 part of functional altogether intercalation organic montmorillonoid and 100 parts of polyamide 6s, BASF AG's manufacturing) melt extrudes granulation, four sections Heating Zone Temperature are respectively 240,260,260 and 250 degree from the opening for feed to the extruder head, and screw speed is 180 rev/mins.Can obtain polyamide 6/laminated nm-silicate composite material.Measure the functional sheet interlayer spacing of intercalation organic montmorillonoid altogether in this material through X-ray diffraction method, the result shows sheet interlayer spacing (as shown in table 1) more than 10 nanometers, this show functional altogether intercalation organic montmorillonoid in the matrix material that makes with the nanoscale homodisperse.Its mechanical property and resistance toheat see Table 1.
Embodiment 2-5
With example 1, wherein functional intercalation organic montmorillonoid content altogether is respectively 3,5,7 and 10 parts.Its sheet interlayer spacing and performance see Table 1.
Sheet interlayer spacing, mechanical property and the thermotolerance of table 1 polyamide 6 nano composite material
Polymeric amide
Embodiment 12345
6
Functional intercalation organic montmorillonoid content altogether
0 1 3 5 7 10
(part)
Sheet interlayer spacing (nanometer)-＞10＞10＞10＞10＞10
Tensile strength (MPa) 56 67 77 87 91 99
Tensile modulus (MPa) 2,400 3,200 3,600 3,900 4,300 4800
Flexural strength (MPa) 98 119 130 140 152 180
Modulus in flexure (MPa) 2,200 2,500 2,800 3,400 3,700 4200
IZOD notched Izod impact strength (Jiao/rice) 64 87 90 116 93 87
Tension set (%) 133 100 67 36 16 11
Heat-drawn wire (degree) (1.85 MPa load) 62 97 120 140 154 163
Above result shows that with the nanoscale homodisperse, the strength and stiffness of nano composite material are much larger than the polyamide 6 bulk material in the material that makes for functional intercalation organic montmorillonoid altogether, and heat-drawn wire has improved 100 degree.In addition, the notched Izod impact strength of nano composite material also is higher than polyamide 6.
Embodiment 6
The method for making of nano composite material is with example 1, and wherein functional intercalation organic montmorillonoid content altogether is 5 parts.It is carried out the water-absorbent test, specimen size: long 12.7 centimetres, wide 2.54 centimetres, thick 3 millimeters.Sample is made by the injector injection.Sample is fully dried, weigh, place the water of 20 degree, at set intervals, sample is taken out and rapidly it dried, weigh.Its water-absorbent is shown in table 2.
Embodiment 7
The method for making of nano composite material is with example 1, and wherein functional intercalation organic montmorillonoid content altogether is 10 parts.It is carried out the water-absorbent test, and its water-absorbent also is shown in table 2.
The water regain of table 2 polyamide 6 nano composite material
Polyamide 6 water regain embodiment 6 water regain embodiment 7 water regains
Absorbent time (minute)
(gram/100 gram samples) (gram/100 gram samples) (gram/100 gram samples)
0 0 0 0
30 0.6 0.5 0.2
60 1.0 0.6 0.3
200 2.1 1.1 0.7
300 3.0 1.3 1.0
900 5.0 2.1 1.7
1440 5.2 2.6 2.1
2500 5.7 3.5 2.8
3600 6.1 4.2 3.4
10000 6.1 4.2 3.4
By the result as can be known, no matter be before suction is saturated or saturated water adsorptive value, the water-absorbent of nano composite material significantly is lower than the polyamide 6 bulk material.
Embodiment 8
The method for making of nano composite material is with example 1, and wherein functional intercalation organic montmorillonoid content altogether is 5 parts.Be made into thickness and be 1 millimeter sample, utilize X-ray diffraction to test its degree of crystallinity and crystalline structure, it the results are shown in table 3.
The degree of crystallinity and the crystalline structure of table 3 polyamide 6 nano composite material
Polyamide 6 embodiment 8
Degree of crystallinity (%) 26 53
Crystalline structure (alpha-crystal form content/γ crystal formation content) 10,0/0 4/96
By above result as can be known, the degree of crystallinity of nano composite material is far above the polyamide 6 bulk material, and its crystallizing field is mainly the γ crystal formation.High degree of crystallinity and γ crystal formation help improving the mechanical property of material and reduce water-absorbent.
Embodiment 9
With 100 parts sodium-based montmorillonite, stirred 2 hours earlier, form the stable suspersion system 1000 parts water high speeds.Then 30 parts cetyl trimethylammonium bromide is joined and continue in the suspension to stir 2 hours.After treating that ion exchange reaction is finished, leave standstill and suspension was fully precipitated in 24 hours, remove supernatant liquid and obtain mud shape mixture, (CIBA-GEIGY company makes with 40 parts of bisphenol A type epoxy resin ARALDITE GY240 then, molecular weight 340-380, oxirane value 0.52-0.56) join in the mud shape mixture and fully stirred 2 hours.At last it is dehydrated and product is crushed to 200-400 order particle diameter, promptly obtain functional intercalation organic montmorillonoid altogether.On the twin screw extruder of 30 mm dias, with 5 parts of functional intercalation organic montmorillonoid and 100 parts of polyamide 6s altogether, 6 (polymeric amide-6 trade mark is ULTRAMID A3, BASF AG's manufacturing) melt extrudes granulation, four sections Heating Zone Temperature are respectively 275,280,280 and 270 degree from the opening for feed to the extruder head, screw speed is 180 rev/mins, can obtain polyamide 6,6/ laminated nm-silicate composite material.Measure the functional sheet interlayer spacing of intercalation organic montmorillonoid altogether in this material through X-ray diffraction method, the result shows sheet interlayer spacing (as shown in table 4) more than 10 nanometers, this show functional altogether intercalation organic montmorillonoid in the matrix material that makes with the nanoscale homodisperse.Its mechanical property and resistance toheat see Table 4.
Embodiment 10
With example 9, wherein functional intercalation organic montmorillonoid content altogether is 10 parts.Its sheet interlayer spacing and performance see Table 4.
Table 4 polyamide 6, the sheet interlayer spacing of 6 nano composite materials, mechanical property and thermotolerance
The embodiment polyamide 6,69 10
Functional intercalation organic montmorillonoid content (part) 05 10 altogether
Sheet interlayer spacing (nanometer)-＞10＞10
Tensile strength (MPa) 81 98 108
Tensile modulus (MPa) 3,010 4,600 5300
Flexural strength (MPa) 112 149 180
Modulus in flexure (MPa) 3,200 4,200 4800
IZOD notched Izod impact strength (Jiao/rice) 96 147 140
Tension set (%) 9 6.5 5
Heat-drawn wire (degree) (1.85 MPa load) 75 133 167
Above result shows, with the nanoscale homodisperse, the strength and stiffness of nano composite material are much larger than polyamide 6 in the material that makes for functional intercalation organic montmorillonoid altogether, 6 bulk materials, and heat-drawn wire has improved nearly 100 degree.In addition, the notched Izod impact strength of nano composite material also is higher than polyamide 6,6.
Claims (7)
1. a polymeric amide/functional intercalation altogether nano composite material of layered silicate material that organises, this functional altogether intercalation organise layered silicate material by inorganic laminated silicate material is carried out organic cation ammonium salt and epoxy compounds altogether intercalation organise to handle and obtain, it is characterized in that the feed composition of described nano composite material and content are as follows: (weight part)
Polymeric amide 100
Layered silicate material 0.1-30
Organic cation ammonium salt 0.1-50
Epoxy compounds 0.1-50.
2. a kind of polymeric amide according to claim 1/functional is the organise nano composite material of layered silicate material of intercalation altogether, it is characterized in that described inorganic laminated silicate material is meant the material with sheet crystalline structure, lamellar spacing is between 0.5 nanometer to 2 nanometer, and lamella length and width are between 10 nanometer to 1000 nanometers; This type of material comprises sodium-based montmorillonite, calcium-base montmorillonite, magnesium base montmorillonite, polynite class, nontronite, beidellite, rich volchonskoite, hectorite, saponite, sauconite, stevensite, bentonite, illite, kaolin, polynite and illitic mixture, except above natural mineral, artificial hydro-thermal synthetic polynite and saponite are also included among the inorganic laminated silicate material of indication of the present invention.
3. a kind of polymeric amide according to claim 1/functional is the organise nano composite material of layered silicate material of intercalation altogether, it is characterized in that described organic cation ammonium salt has following structure: NH
3 +R
1Or NH
2 +R
2R
3Or NH
+R
4R
5R
6Or N
+R
7R
8R
9R
10, R wherein
1To R
10Be aromatic base or alkyl, can be the same or different to each other.
4. a kind of polymeric amide according to claim 1/functional is the organise nano composite material of layered silicate material of intercalation altogether, it is characterized in that described epoxy compounds comprises organic monomer, oligopolymer and superpolymer, contain an epoxide group on the epoxy compounds molecular chain at least.
5. a kind of polymeric amide according to claim 1/functional is the organise nano composite material of layered silicate material of intercalation altogether, it is characterized in that described polymeric amide comprises polyamide 6, polyamide 6,6, polymeric amide 11, polymeric amide 12, polymeric amide 4,6 and polymeric amide 10.
6. a kind of polymeric amide according to claim 1/functional is the organise nano composite material of layered silicate material of intercalation altogether, it is characterized in that the functional altogether intercalation layered silicate material preparation method that organises is as follows: earlier with the inorganic laminated silicate material of 0.1-30 part, water high speed 1-1000 part stirs, and forms the stable suspersion system; Then the organic cation ammonium salt of 0.1-50 part is joined and continue in the suspension to stir, utilize ion exchange reaction to make ammonium salt insert the silicate plate interlayer and the silicate plate laminar surface is organised; After treating that permutoid reaction is finished, leave standstill silicate material is fully precipitated, remove supernatant liquid and obtain mud shape mixture, the epoxy compounds of 0.1-50 part is joined continue in the mud shape mixture fully to stir then; At last it is dehydrated and product is crushed to 200-400 order particle diameter, this final product is the functional intercalation altogether layered silicate material that organises.
7. a kind of polymeric amide according to claim 1/functional is the organise preparation method of nano composite material of layered silicate material of intercalation altogether, it is characterized in that the nano composite material preparation method is as follows: in shearing force being provided simultaneously and polymeric amide being heated to equipment more than the fusing point, with the functional altogether intercalation of 0.1-30 part organise layered silicate material and 100 parts of molten polyamide extruding pelletizations, can obtain nano-class polyamide/laminated silicate composition.
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| CN102286199B (en) * | 2010-06-21 | 2013-05-01 | 国家复合改性聚合物材料工程技术研究中心 | Formula of composite low-melting-point nylon 6 and preparation method |
| CN103160183B (en) * | 2013-04-03 | 2015-04-22 | 哈尔滨理工大学 | Preparation method of nano anticorona varnish |
| CN103232716A (en) * | 2013-05-14 | 2013-08-07 | 甘肃省交通规划勘察设计院有限责任公司 | Preparation method of petroleum asphalt anti-stripping agent suitable for acid stone |
| CN105504802A (en) * | 2015-12-30 | 2016-04-20 | 浙江博尼锦纶科技有限公司 | Organic magnesium lithium silicate-nylon 6 composite material and preparation method thereof |
| CN107099116A (en) * | 2017-05-18 | 2017-08-29 | 湖南省达琪新材料有限公司 | The preparation method of polyamide polyamines intercalation phyllosilicate composite |
| CN108192338A (en) * | 2017-12-27 | 2018-06-22 | 浙江普利特新材料有限公司 | A kind of high intensity, high-modulus, bloom metallic luster, it is repeatable utilize exempt from spray nylon material and preparation method thereof |
| CN110437610A (en) * | 2019-08-14 | 2019-11-12 | 天津长芦海晶集团有限公司 | Using polyamide 6 as clay polymer composite of matrix and preparation method thereof |
| CN114507438A (en) * | 2021-09-02 | 2022-05-17 | 广东泰塑新材料科技有限公司 | Polyamide and silicate composite material and preparation method thereof |
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