CN1454935A - Nylon 66/montmorillonite nano composite material and preparing method thereof - Google Patents
Nylon 66/montmorillonite nano composite material and preparing method thereof Download PDFInfo
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- CN1454935A CN1454935A CN 03106526 CN03106526A CN1454935A CN 1454935 A CN1454935 A CN 1454935A CN 03106526 CN03106526 CN 03106526 CN 03106526 A CN03106526 A CN 03106526A CN 1454935 A CN1454935 A CN 1454935A
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Abstract
The present invention provides a nylon 66 and imvite nano composite material and its preparation method. Its raw material includes nylon 66, imvite, intercalation ion exchange, modifying agent, and its preparation method is characterized by that the imvite after which is treated by intercalation ion exchange and modifying agent and nylon 66 granules are mixed to obtain the invented product wich greatly raised heat-resisting temperature and good comprehensive performance of nano composite material.
Description
Technical field
The present invention relates to a kind of nano composite material and preparation method thereof, be specifically related to a kind of nano composite material of forming by nylon 66 and polynite and preparation method thereof.
Background technology
Good characteristics such as that polymeric amide has is high-strength, wear-resisting, self-lubricating, output occupies first of the five large-engineering plastics over the years, replacing steady growth always aspect traditional structural metallic materials, obtained widespread use as fields such as trolley part, mechanical part, electronic apparatuss.But Polyamide Engineering Plastic thermotolerance and acid resistance are relatively poor; Shock strength is on the low side under dry state and low temperature; Water-intake rate is big, influences product size stability and electrical property, and this has limited its application.Since Japan's report in 1987 prepares nylon 6/ polynite hybrid materials with the intercalation polymeric method, because nano composite polymer-montmorillonoid material has been realized nanophase homodisperse, strong interfacial bond and self-assembly, have the advantage incomparable (as mechanics, thermal property and the gas barrier property etc. of excellence), therefore receive much concern than conventional polymer/inorganic filler composite material.Domestic and international research Showed Very Brisk to nano composite polymer-montmorillonoid material; U.S. Cornell university, Michigan state university, Japanese ToyotaCenter Research and Development Laboratories, Inc. and Institute of Chemistry, Academia Sinica etc. have prepared polymers of excellent properties/clay nanocomposites such as PET, PBT, Nylon6, PS/ polynite respectively.
Toyota Company has proposed first plastic nano matrix material patent, and develops the nylon nano matrix material cooperatively with company of space portion emerging product (UBE).U.S. RTP company develops a kind of nylon 6/ montmorillonite composite material, and polynite content is 3-5%, adopts the Special Mixed technology that polynite is dispersed in the nylon-6 matrix body with the nanoscale homogeneous, is the ideal material of isolation-type hollow container blowing.Nylon 6/ montmorillonite composite of Japan ユ ニ チ カ company has formed M1030D, M1050B (tension type) and the serial commercially produced product of M1030DT20 (enhancement type).
The chemistry QiZongNeng professor of the institute leader's of the Chinese Academy of Sciences research group obtains following progress at present: the monomer intercalation polycondensation has prepared nylon 6/ Nano composite material of montmorillonite, can increase substantially its heat-drawn wire, enlarge the range of application of material, and the relation of the interlamellar spacing of the carbochain yardstick of intercalator and organo montmorillonite is studied.
Narrated among the patent ZL96105362.3 and a kind ofly produced nylon 6/ clay nanocomposites with the intercalation polymeric method.It combines with polyamide substrate by the layered silicate Coulomb's force, and nanoparticle is dispersed in the polymeric amide with nanoscale, obtains the high-performance nanometer composite polyamide-clay material.
In the nylon-type product, nylon 66 thermotolerance height, shaping speed is fast, and rigidity is big, has therefore worldwide obtained using widely.Yet in above patent and the bibliographical information, all do not relate to the development of nylon 66/ Nano composite material of montmorillonite.This is because nylon 66 exists than big-difference on structure properties with nylon 6, such as the hydrogen bond density of nylon 66 is 100%, and the hydrogen bond density of nylon 6 only is 50%; The processing temperature of nylon 66 is 260～280 ℃, and the processing temperature of nylon 6 only is 210～230 ℃.The organo montmorillonite heat decomposition temperature that makes according to the method for in the past patent and bibliographical information is lower, only there are 250～270 ℃, can decompose in a large number in the course of processing when being used for nylon 66, this not only can influence the bonding interface effect of polynite and nylon 66 matrixes, and in Nylon 66, introduced impurity, influenced the physical and mechanical properties of nylon 66.
Summary of the invention
The purpose of this invention is to provide a kind of based on nano composite polymer-montmorillonoid material nylon 66 and polynite, that over-all properties is more excellent and preparation method thereof.
Technical scheme provided by the present invention is as follows:
A kind of is the nano composite material raw material that main raw material is made by nylon 66 and polynite, and the feed composition of this matrix material and content (weight part) are:
Nylon 66 particles 100
Polynite 0.50-20
Intercalation ion-exchanger 0.25-10
Properties-correcting agent 0.20-10
Wherein: the polynite raw material is for containing 85-95% polynite silico-aluminate, and particle diameter is the 100-500 order, and its cation exchange capacity (CEC) is 50-200meq/100g.
The disperse phase yardstick of above-mentioned polynite raw material is the 10-80 nanometer.
A kind of method for preparing above-mentioned nylon 66/ Nano composite material of montmorillonite is:
A, elder generation put into 10-1000 part water mechanical stirring with the polynite of 0.50-20 part, form stable suspension, heating in water bath adds 0.25-10 part intercalation ion-exchanger and carries out cation exchange reaction to 50-90 ℃, suction filtration after exchange is finished, and to filtrate, do not have Br with the distilled water wash throw out
-Ion;
B, 0.20-10 part properties-correcting agent is added in the sulphuric acid soln that 10-300 part concentration is 50～80% aqueous formic acid or 50～98%, under bath temperature 50-90 ℃, be made into mixed solution;
C, the throw out that a is obtained add 5-150 part water, in the mixed solution that the back adding b that stirs obtains, change in 150-700 part water after restir is even and precipitate, suction filtration once more, and extremely neutral with the distilled water wash throw out, formic acid or sulfuric acid are removed, obtain modified organo montmorillonite;
D, with c obtain with the modified organo montmorillonite heat drying, grind, sieve after, add 100 parts of nylon 66 particles, mix, on twin screw extruder, extrude then, granulation, promptly obtain nylon 66/ Nano composite material of montmorillonite.
The used intercalation ion-exchanger of the present invention is an organic amine, as palmityl trimethyl ammonium chloride and brometo de amonio, octadecyl trimethyl ammonium chloride, dodecyl benzyl dimethyl ammonium chloride, distearyl dimethyl ammonium chloride, Dodecyl trimethyl ammonium chloride and brometo de amonio thereof, it can use separately or be used.
The used properties-correcting agent of the present invention is nylon 6, nylon 66, nylon 1010.Its effect is under 50～90 ℃ of bath temperatures properties-correcting agent to be dissolved in dispersion medium (II) wiring solution-forming (III), then with exchanged cationic polynite reactant aqueous solution.Ion-exchanger is cemented out in the middle of the montmorillonite layer, thereby increase substantially the heat decomposition temperature of new modified organo montmorillonite, make in its processing treatment that can be used for nylon 66.In addition, because properties-correcting agent has and the similar or identical constitutional features of nylon 66 matrix resins, therefore organo montmorillonite and nylon 66 matrixes after the modification have better consistency and bonding interface effect, help organo montmorillonite homodisperse in Nylon 66, thereby can increase substantially the mechanical property of nylon 66 and thermal property etc.
The used nylon 66 of the present invention is the Industrial products grade nylon 66, can select the different trades mark for use according to purposes.
The used polynite of the present invention is the nonmetal stratiform silicate minerals of a class, main mineralogical composition is the lamellar aluminosilicate that contains the 85-95% polynite, its unit cell is formed by carrying the layer of aluminum oxygen octahedra secretly in the middle of the two-layer silicon-oxy tetrahedron, connect by shared Sauerstoffatom between the two, the unit cell surface-area is 2 * 5.15 * 8.9
2, the heavy 700-800 gram/mol of structure cell.The lamellar spacing of polynite crystal layer is 1.5-2nm.The lamella internal surface has negative charge, each negative charge footprint area 25-200
2, specific surface area 700-800 rice
2/ gram, interlayer cation Na
+, Ca
2+, Mg
2+Deng being the interchangeability positively charged ion, adopt organic ammonium and polynite to carry out can enlarging sheet interlayer spacing after the permutoid reaction, help polymer molecular chain and insert montmorillonite layer, to form nano composite material.Selected polynite should have cation exchange capacity (CEC) 50-200meq/100g, is preferably 90-110meq/100g, and wherein cation exchange capacity is at 70-90meq/100g.The disperse phase yardstick of polynite is the 10-80 nanometer.
Described polynite preferably is crushed to suitable particle diameter, and available ball mill, vibration mill, jet mill etc. are ground into desirable particle size to polynite, and general particle diameter should be the 100-500 order.
Compared with prior art, the invention has the advantages that:
1, nylon 66/ Nano composite material of montmorillonite provided by the invention, the polynite disperse phase reaches 10～50 nanoscales, has very large interfacial area.Inorganic disperse phase and polymer-based carbon body interface have the ideal adhesiveproperties, can eliminate inorganics and polymeric matrix two material thermal expansivity mismatch problems, give full play to the excellent mechanical property of inorganics intrinsic, high heat resistance.
2, nylon 66/ Nano composite material of montmorillonite provided by the invention, its physical and mechanical properties increases substantially, and is higher than like products such as nylon 6/ Nano composite material of montmorillonite, is with a wide range of applications.This raising can owing to the dispersion of polynite wafer nanoscale in the Nylon 66 matrix and with good consistency of nylon 66 matrixes and extremely strong interaction.
3, the preparation method of nylon 66/ Nano composite material of montmorillonite provided by the invention, the modified organo montmorillonite lattice spacing that makes is bigger, is about 3～6 nanometers, and this makes the dispersion of modified organo montmorillonite in the polymeric resin matrix become to carry out easily.According to " polymer material science and engineering " (Vol.14.No.3.) " clay/nylon 6 intercalation compound synthetic with characterize " can carry out Theoretical Calculation to the required power that expands of montmorillonite layer in the organ-mmt process.Under the Van der Waals force effect, the energy that clay crystal layer per unit area has is:
In the formula, δ is a clay crystal layer thickness; H is a lattice spacing, h=d
001-δ; A is the Hamaker constant, A=9.5 * 10
-20J, and think that it is the peculiar constant of material.So, for the clay lattice spacing being pushed open the necessary power F of distance of Δ h
aFor:
When getting δ=1nm, and clay crystal layer basal plane spacing is when being 1.2nm, and reactive force is about 1500 * 1.013 * 10 between clay seam
5Pa; 1.5nm the time be about 80 * 1.013 * 10
5Pa; 2.0nm the time be about 7 * 1.013 * 10
5Pa; 4.0nm the time be about 3.8 * 1.013 * 10
5Pa.As seen when polynite lattice spacing during,, but descend soon though it is still very big to push the required power of crystal layer sheet interlayer spacing open greater than 1.2nm.This shows that when organic polynite lattice spacing was 3～6 nanometers, it was very little to push the required power of crystal layer lamella open, this will help the homodisperse of montmorillonite layer in polymer resin matrix.
4, the preparation method of nylon 66/ Nano composite material of montmorillonite provided by the invention, the modified organo montmorillonite heat decomposition temperature height that makes, the polynite heat decomposition temperature of handling than organic ammonium class is high 100 ℃ approximately, and this has widened the work range that organo montmorillonite is suitable for greatly.
Embodiment
Getting cation exchange capacity is the polynite 3g of 100meq/100g, adds water 100g, and after waiting to be uniformly dispersed, high-speed stirring 1 hour in 1 week of ageing, obtains stable montmorillonite suspension liquid A; This suspending liquid A is warming up to 70 ℃ under mechanical agitation.The 1.5g cetyl trimethylammonium bromide is dissolved in the 20g warm water, slowly adds in the suspending liquid A, vigorous stirring keeps isothermal reaction 3 hours.After reaction finished, suction filtration did not also have Br with the distilled water wash product to filtrate
-Ion (available AgNO
3The solution check), leach adding 15g water wiring solution-forming B in the thing to this again.
Get nylon 6 particle 1.5g and join among 88% the formic acid solution 15ml, be warming up to about 70 ℃, stir and make nylon 6 dissolving wiring solution-forming C.
The formic acid solution 6ml of adding 88% in solution B, stirred 2 minutes, to be mixedly join in the solution C after evenly, vigorous stirring 3 minutes, stopping then stirring changes over to mixing solutions in the 55g distilled water under mechanical agitation, make its precipitation, last suction filtration, and to clean to filtrate with distilled water be neutral.With product drying, grinding, mistake 360 mesh sieves, obtain modified organo montmorillonite D.
Get 100g Industrial products grade nylon 66 particle, add a small amount of white oil, and modified organo montmorillonite D is added, vigorous stirring mixes it.Make mixture enter twin screw extruder then, extrude, granulation, obtain nylon 66/ Nano composite material of montmorillonite.
Prepared modified organo montmorillonite D (Modified Montmorillonite, be MMMT), only use cetyl trimethylammonium bromide montmorillonite modified (Organnomontmorillonite, be OMMT) and sodium-based montmorillonite (Na-Montmorillonite, be MMT) performance through TG, DTG and x-ray diffraction experiment analysis, data see Table 1..
Every performance of the polynite of table 1. embodiment
The high lattice spacing of embodiment thermal weight loss (%) heat decomposition temperature (nm)
(℃)
MMMT 49.12 337.7 3.91
OMMT 33.43 254.4，268 4.20
MMT 3.20 -- 1.62
This nylon 66/ Nano composite material of montmorillonite is measured the d of polynite through X-ray diffraction
001The diffraction peak of interplanar distance and transmission electron microscope observation montmorillonite layer thickness, show polynite in matrix material with the nanoscale homodisperse, its mechanical property sees Table 2..
Every performance of nylon 66/ Nano composite material of montmorillonite of table 2. embodiment
The strong Young mould bending die that stretches impacts heat-flash distortion temperature
Embodiment measure the * degree (℃)
(MPa) (GPa) (GPa) (kJ/m
2)
Nylon 66 74.61 2.76 253 3.63 57.2
Nylon 66/MMT------3.00 63.0
(6phr)
Nylon 66/MMMT 84.21 3.80 3.08 3.23 89.0**
Data when (5phr) these data of * notched Izod impact strength * * are 7phr for modified organo montmorillonite content
Common fillers is filled the general tensile strength in back all obvious decline, but nanomaterial-filled matrix material, its tensile strength can increase to some extent.From table 2. data as can be seen, the tensile strength of nylon 66/ Nano composite material of montmorillonite is 1.13 times of pure nylon 66.It can also be seen that from table 2. tensile modulus of nylon 66/ Nano composite material of montmorillonite has improved 58%.Modulus in flexure has improved 30%.
Heat-drawn wire claims heat distortion temperature again, is a kind of characterization parameter of polymkeric substance as the ceiling temperature of structured material use.In matrix material, heat-drawn wire is that constant speed is heated under specified load, along with temperature raises, and the temperature when sample reaches the regulation distortion.The heat-drawn wire of matrix material is relevant with the second-order transition temperature of resin matrix, also is related to the use temperature of matrix material, and therefore important and practical meanings is arranged.Can find out that from table 2. when adding the 7phr polynite, heat-drawn wire has improved nearly 32 ℃, be elevated to 89.0 ℃ by 57.2 ℃ of pure nylon 66.
Notched Izod impact strength is mainly relevant with the ability of material opposing crack propagation.By table 2. as seen, the shock strength of matrix material slightly descends, but reduces seldom, and impelling strength keeps substantially.
Claims (7)
1, a kind of nylon 66/ Nano composite material of montmorillonite mainly is made up of nylon 66 and polynite, it is characterized in that: the feed composition of this matrix material and content (weight part) are:
Nylon 66 particles 100
Polynite 0.50-20
Intercalation ion-exchanger 0.25-10
Properties-correcting agent 0.20-10
2, according to described nylon 66/ Nano composite material of montmorillonite of claim 1, it is characterized in that: described polynite raw material is for containing 85-95% polynite silico-aluminate, and particle diameter is the 100-500 order, and its cation exchange capacity (CEC) is 50-200meq/100g.
3, according to claim 1 or 2 described nylon 66/ Nano composite material of montmorillonite, it is characterized in that: the disperse phase yardstick of described polynite is the 10-80 nanometer.
4, a kind of preparation is characterized in that as the method for described nylon 66/ Nano composite material of montmorillonite of claim 1-3:
A, elder generation put into 10-1000 part water mechanical stirring with the polynite of 0.50-20 part, form stable suspension, heating in water bath adds 0.25-10 part intercalation ion-exchanger and carries out cation exchange reaction to 50-90 ℃, suction filtration after exchange is finished, and to filtrate, do not have Br with the distilled water wash throw out
-Ion;
B, 0.20-10 part properties-correcting agent is added in the sulphuric acid soln that 10-300 part concentration is 50～80% aqueous formic acid or 50～98%, under bath temperature 50-90 ℃, be made into mixed solution;
C, the throw out that a is obtained add 5-150 part water, in the mixed solution that the back adding b that stirs obtains, change in 150-700 part water after restir is even and precipitate, suction filtration once more, and extremely neutral with the distilled water wash throw out, formic acid or sulfuric acid are removed, obtain modified organo montmorillonite;
D, the modified organo montmorillonite heat drying that c is obtained, grind, sieve after, add 100 parts of nylon 66 particles, mix, on twin screw extruder, extrude then, granulation, promptly obtain nylon 66/ Nano composite material of montmorillonite.
5, nylon 66/ Nano composite material of montmorillonite preparation method according to claim 4 is characterized in that the cation exchange capacity (CEC) of described polynite is preferably 90～110meq/100g.
6, according to described nylon 66/ Nanometer Composite Material Of Montmorillonite And Its Preparation Method of claim 1-5, it is characterized in that described intercalation ion-exchanger is an organic amine, as palmityl trimethyl ammonium chloride and brometo de amonio, octadecyl trimethyl ammonium chloride, dodecyl benzyl dimethyl ammonium chloride, distearyl dimethyl ammonium chloride, Dodecyl trimethyl ammonium chloride and brometo de amonio thereof, it can use separately or be used.
7,, it is characterized in that described properties-correcting agent is nylon 6, nylon 66, nylon 1010 according to described nylon 66/ Nanometer Composite Material Of Montmorillonite And Its Preparation Method of claim 1-6.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100348665C (en) * | 2006-04-28 | 2007-11-14 | 湘潭大学 | Process for in-situ polymerization preparation of nylon 6/epoxy resin/silicon dioxide nano composite materials |
| CN100500764C (en) * | 2007-06-29 | 2009-06-17 | 浙江工业大学 | Preparation method of polyamide/nano montmorillonite masterbatch |
| CN101832429A (en) * | 2010-04-19 | 2010-09-15 | 黄中南 | Three-layer composite pipe for use in water conservancy dredging and preparation method thereof |
| CN101564874B (en) * | 2009-05-27 | 2012-07-04 | 靳柱山 | Method for preparing nanometer heat-insulation composite material |
| CN101058678B (en) * | 2007-05-29 | 2013-03-13 | 株洲时代新材料科技股份有限公司 | Large interlamellar spacing and high activity modified calcium-base montmorillonite and preparation method thereof |
| CN101724414B (en) * | 2009-12-30 | 2013-06-05 | 江西固康新材料有限公司 | Nano fire-retarding additive and preparation method thereof |
| CN104479350A (en) * | 2014-12-29 | 2015-04-01 | 江西固康新材料有限公司 | Halogen-free flame-retarded polycaprolactam compound with low smoke and extremely low odor |
| CN104710781A (en) * | 2013-12-17 | 2015-06-17 | 上海杰事杰新材料(集团)股份有限公司 | Co-intercalating agent modified montmorillonite/nylon 610 T composite material and preparation method thereof |
| CN108239390A (en) * | 2016-12-23 | 2018-07-03 | 惠州市良化新材料有限公司 | A kind of PA6 alloy materials of toughening modifying and preparation method thereof |
| CN111070568A (en) * | 2019-12-27 | 2020-04-28 | 苏州耐思特塑胶有限公司 | Water-assisted injection molding processing technology of plastic part |
| CN112029313A (en) * | 2020-08-19 | 2020-12-04 | 宫伟鹏 | Preparation method and application of nano organic montmorillonite |
-
2003
- 2003-02-26 CN CN 03106526 patent/CN1235975C/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100348665C (en) * | 2006-04-28 | 2007-11-14 | 湘潭大学 | Process for in-situ polymerization preparation of nylon 6/epoxy resin/silicon dioxide nano composite materials |
| CN101058678B (en) * | 2007-05-29 | 2013-03-13 | 株洲时代新材料科技股份有限公司 | Large interlamellar spacing and high activity modified calcium-base montmorillonite and preparation method thereof |
| CN100500764C (en) * | 2007-06-29 | 2009-06-17 | 浙江工业大学 | Preparation method of polyamide/nano montmorillonite masterbatch |
| CN101564874B (en) * | 2009-05-27 | 2012-07-04 | 靳柱山 | Method for preparing nanometer heat-insulation composite material |
| CN101724414B (en) * | 2009-12-30 | 2013-06-05 | 江西固康新材料有限公司 | Nano fire-retarding additive and preparation method thereof |
| CN101832429A (en) * | 2010-04-19 | 2010-09-15 | 黄中南 | Three-layer composite pipe for use in water conservancy dredging and preparation method thereof |
| CN104710781A (en) * | 2013-12-17 | 2015-06-17 | 上海杰事杰新材料(集团)股份有限公司 | Co-intercalating agent modified montmorillonite/nylon 610 T composite material and preparation method thereof |
| CN104479350A (en) * | 2014-12-29 | 2015-04-01 | 江西固康新材料有限公司 | Halogen-free flame-retarded polycaprolactam compound with low smoke and extremely low odor |
| CN108239390A (en) * | 2016-12-23 | 2018-07-03 | 惠州市良化新材料有限公司 | A kind of PA6 alloy materials of toughening modifying and preparation method thereof |
| CN111070568A (en) * | 2019-12-27 | 2020-04-28 | 苏州耐思特塑胶有限公司 | Water-assisted injection molding processing technology of plastic part |
| CN112029313A (en) * | 2020-08-19 | 2020-12-04 | 宫伟鹏 | Preparation method and application of nano organic montmorillonite |
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