CN1491990A - Nylon 1010/montmorillonite nano composite material and its preparing method - Google Patents
Nylon 1010/montmorillonite nano composite material and its preparing method Download PDFInfo
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Abstract
The present invention provides a kind of nano composite nylon 1010/montmorillonite material and its preparation process. The materials includes nylon 1010, montmorillonite, intercalation ion exchange agent, etc. Montmorillonite after being processed with intercalation ion exchange agent is suction filtered, cleaned, dried, ground, sieved, and then mixed with nylon 1010 particles, and the mixture is extruded, palletized to obtain nano composite nylon 1010/montmorillonite material; or, the sieved montmorillonite, nylon 1010 monomer and other assistants are mixed, added with dispersin medium and polymerized to obtain nano composite nylon 1010/montmorillonite material. The organic matter modification of montmorillonite can raise the heat resisting temperature greatly and the nano composite material has excellent comprehensive performance.
Description
Technical field:
The present invention relates to a kind of nylon 1010/Nanometer Composite Material Of Montmorillonite And Its Preparation Method.Be specifically related to a kind of nano composite material of forming by nylon 1010 and polynite and preparation method thereof.
Background technology:
Nylon 1010 is Chinese distinctive nylon kind.The raw material Viscotrol C of nylon 1010 comes from Semen Ricini.Castor-oil plant is very wide in China place of production, thereby makes the production of nylon 1010 have abundant raw material sources.Nylon 1010 not only can be made synthon, and can be processed into plastics, replaces noble metals such as non-ferrous metal copper and stainless steel on engineering, is used for the manufacturing machine part.Nylon 1010 occupies considerable status in civilian, national defense industry.But nylon 1010 is also bigger as other nylon product water absorbability, and thermal expansivity is more much bigger than metal, and thermal conductivity is also poor.At the weakness of nylon 1010, continue to bring out with elastomerics, inelastic body tenacity increased nylon, thermotolerance nylon and the inorganics filled Reinforced Nylon new variety that are modified as purpose in recent years.A kind of modification of nylon 1010 also is provided among the patent CN 1039825A.It is to be formed by nylon 1010 and the polyethylene copolymerization that has the polarity side chain.The low-temperature flexibility of this modifying polyamide 1010 significantly improves, and has good low-temperature shock strength and elongation at break.But comparing with the method for modifying of routine, advanced nanotechnology has irreplaceable superiority.Japanese Toyota Company had proposed first plastic nano matrix material patent in 1987, and developed the nylon/montmorillonoid nano composite material cooperatively with company of space portion emerging product (UBE).The nylon/montmorillonoid nano composite material has than the excellent a lot of mechanical property of traditional packing material, thermal characteristics, barrier property, anisotropy etc.The inorganic components content of this material is few, and weight ratio tradition packing material is light.Aspect processing, can adopt traditional working method, finished product also can be made fiber or film, thereby the nylon/montmorillonoid nano composite material is with a wide range of applications, and what have has commercial applications.For example, Toyota Motor company has been used for nylon 6/ Nano composite material of montmorillonite to make the accessory of motor car engine, because it has high-modulus and high thermal transition temperature, product has high hardness, good thermostability, and not distortion, weight also alleviates 25%, so nylon 6/ Nano composite material of montmorillonite is first mass-produced organic-inorganic nanocomposite.Therefore adopt nanotechnology imperative to the research that nylon 1010 carries out modification.Nylon 1010/Nano composite material of montmorillonite also will improve the physical and mechanical properties of nylon 1010 greatly, constantly expand the Application Areas of nylon 1010.
Summary of the invention:
Nylon 1010/the Nanometer Composite Material Of Montmorillonite And Its Preparation Method that the purpose of this invention is to provide the high organic montmorillonoid of a kind of heat decomposition temperature and a kind of excellent combination property.
Technical scheme of the present invention is:
Nylon 1010/Nano composite material of montmorillonite mainly is made up of nylon 1010, polynite, copolymerization constituent monomers, intercalation ion-exchanger etc., and each component according to weight part is:
Nylon 1010 monomer 80～110
Copolymerization constituent monomers 0～30
Polynite 0.50～20
Intercalation ion-exchanger 0.25～10
Initiator 0～20
Protonating agent 0～1.0
Additive 0～5
Dispersion medium 0～120
The preparation method of nylon 1010/Nano composite material of montmorillonite is:
A. with 0.50～20 part of polynite mechanical stirring in the presence of deionized water, form stable suspension, heating in water bath to 50～90 ℃ or at room temperature, add 0.25～10 part of intercalation ion-exchanger and carry out cation exchange reaction, suction filtration, use deionized water washing sediment, unreacted ion-exchanger is removed;
B. with a products therefrom heat drying, grind, sieve, add 100 parts of nylon 1010 particles, mix, on twin screw extruder, extrude, granulation, promptly get product.
The preparation method of nylon 1010/Nano composite material of montmorillonite can also be:
A. with 0.50～20 part of polynite mechanical stirring in the presence of deionized water, form stable suspension, heating in water bath to 50～90 ℃ or at room temperature, add 0.25～10 part of intercalation ion-exchanger and carry out cation exchange reaction, suction filtration, use deionized water washing sediment, unreacted ion-exchanger is removed;
B. will after 0.5～20 part of intercalator montmorillonite modified and 100 parts of nylon 1010 monomers grindings, mix; add 5～30 parts of copolymerization constituent monomers, 0.05～5 part of additive, 0.001～1 part of protonating agent and 0.01～20 part of initiator; put into polymeric kettle after mixing evenly; add 1～120 part of dispersion medium; under CO 2 gas-shielded, be warming up to 190～240 ℃ of polymerizations 4～6 hours, promptly get product.
The invention has the advantages that:
1, the preparation method of nylon 1010/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.The fastest heat decomposition temperature of gained modified organo montmorillonite is higher, particularly adopt the common organo montmorillonite of handling of Polyvinylpyrolidone (PVP) or itself and organic amine, its the fastest heat decomposition temperature is respectively 451.6 ℃ and 439.1 ℃, has almost reached subside 500 ℃～600 ℃ of temperature of polynite crystalline.This makes various organo montmorillonites all applicable to the machine-shaping of nylon 1010, has widened the work range that organo montmorillonite is suitable for greatly.
2, nylon 1010/Nano composite material of montmorillonite of the present 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.
3, nylon 1010/Nano composite material of montmorillonite of the present invention, its physical and mechanical properties improves a lot.This raising can owing to the dispersion of polynite wafer nanoscale in the nylon 1010 resin matrix and with good consistency of nylon 1010 matrix and extremely strong interaction.
Embodiment:
The used nylon 1010 of the present invention is an Industrial products level nylon 1010, can select the different trades mark for use according to purposes; Used nylon 1010 monomer is the nylon 1010 salt of commercial grade.
Used polynite is the nonmetal stratiform silicate minerals of a class, and main mineralogical composition is the lamellar aluminosilicate that contains 85～93% polynites, and the lamellar spacing of crystal layer is 1.5-2nm, and 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.The cation exchange capacity of selected polynite (CEC) is 50-200meq/100g, is preferably 90～110meq/100g, and wherein the sodium ion exchange capacity is at 70-90meq/100g.When CEC greater than 200meq/100g, high interlayer Coulomb's force makes that polynite is difficult for being dispersed in the polymeric matrix with the nano level yardstick; When exchange capacity is lower than 50meq/100g, polynite can not interact with the polyamide substrate resin effectively, thereby is not enough to guarantee the consistency of polynite and polymeric matrix, makes polynite be difficult for being dispersed in the polymeric matrix equally.
Polynite preferably is crushed to suitable particle diameter, available ball mill, vibration mill, jet mill etc. are ground into desirable particle size to polynite, general particle diameter should be at 200～400 orders, thickness of clay soil is 9.6 , interfloor distance is 2～5 , after modification was handled, the clay interfloor distance was at least 20 .The clay interfloor distance is big more, and mechanical property and resistance toheat are improved big more.
Used polynite content is 0.50～20 (weight part).When content is lower than 0.50 part, polynite is not enough to produce enough enhancements; When content surpasses 20 parts, polynite will be reunited in a large number, influence the performance of material.In the present invention, the optimum content scope of polynite is 1～10 part.
Used intercalation ion-exchanger is an organic amine, pyridines, phenols, alcohols, the ester class, amides, carboxylic-acid, organic low molecular or macromolecular compounds such as anhydrides, wherein organic amine is a palmityl trimethyl ammonium chloride, octadecyl trimethyl ammonium chloride, dodecyl benzyl dimethyl ammonium chloride, distearyl dimethyl ammonium chloride, Dodecyl trimethyl ammonium chloride, in the brometo de amonio one or more, pyridines is a Polyvinylpyrolidone (PVP), phenols is a meta-cresol, alcohols is a Virahol, the ester class is a n-butyl acetate, amides is a dimethyl formamide, carboxylic-acid is a citric acid, and anhydrides is a maleic anhydride.These organic low moleculars or macromolecular compound can use separately, also can be used.Because high molecular intercalation ion-exchanger has than the organic low molecular better heat-resisting, therefore higher through the heat decomposition temperature of its montmorillonite modified, make in its processing treatment that can be used for nylon 1010.In addition, the intercalation ion-exchanger has and nylon 1010 matrix resin consistency and bonding interface effect preferably, helps organo montmorillonite homodisperse in the nylon 1010 resin, thereby can increase substantially the mechanical property of nylon 1010 and thermal property etc.
Used copolymerization constituent monomers is a kind of in hexanolactam, spicy inner formyl amine, laurolactam, the butyrolactam, the above-mentioned copolymerization constituent monomers of available commercial grade.
The protonating agent that is adopted is a kind of in phosphorous acid, phosphoric acid, hydrochloric acid, sulfuric acid, sulfonic acid, acetic acid, Tricholroacetic Acid, m-phthalic acid or the phthalic acid.
Used initiator is that 6-aminocaprolc acid, ten diamino acid or carbonatoms are the amino acid of 4-19.
Used additive is polyamines, stablizer, toner, lubricant, toughner, nucleator etc.Its effect is by the control crystal habit of resin and molecular structure and does in order to toughness, the rigidity of improving matrix material with the intercalation of clay and further reduce spherulite size, improves the transparency of matrix material.Polyamines has diamines, as hexanediamine, dodecyl diamines etc.; Or triamine, tetramine, five amine etc.Nucleator can be phosphoric acid salt, hard acid ester salt, talcum powder, disodium phenylphosphate salt etc.Additive can use separately or be used.
The effect of used dispersion medium be promote clay in polymer monomer dispersion and improve heat transfer type etc.Dispersion medium is decided according to clay types, monomer, protonating agent, initiator.Good dispersion medium should make clay disperse easily and have good consistency in monomer, protonating agent, catalyzer.Dispersion medium can be water, ethanol, methyl alcohol, propyl alcohol, Virahol, chloroform, N, dinethylformamide, N,N-dimethylacetamide, acetic acid, fumaric acid, 1,4-butyleneglycol etc.
Following indefiniteness embodiment further illustrates embodiment of the present invention and effect.
Embodiment 1.
With 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 montmorillonite suspension liquid A.
Suspending liquid A is warming up to 70 ℃ under mechanical agitation; The 1.5g cetyl trimethylammonium bromide is dissolved in the 20ml warm water, slowly adds in the suspending liquid A, vigorous stirring keeps isothermal reaction 3 hours; After reaction finished, suction filtration and washed product did not have Br to filtrate
-Ion (available AgNO
3The solution check); To leach thing drying, grinding, cross 360 mesh sieves, get organo montmorillonite, be labeled as OM-01.
Under the room temperature, the 1.5g Polyvinylpyrolidone (PVP) is dissolved in the 20ml deionized water, slowly adds in the suspending liquid A, vigorous stirring was reacted 3 hours.After reaction finished, low temperature was dry down, grind, cross 360 mesh sieves, organo montmorillonite, be labeled as OM-02.
The 3g Polyvinylpyrolidone (PVP) is dissolved in the 30ml deionized water wiring solution-forming B.The 0.5g cetyl trimethylammonium bromide is dissolved in the 5ml warm water, slowly adds in the suspending liquid A, vigorous stirring keeps isothermal reaction 2 hours.Slowly add solution B then, keep constant temperature, high-speed stirring reaction 8 hours.After reaction finished, low temperature was dry down, grind, cross 360 mesh sieves, organo montmorillonite, be labeled as OM-03.
Section of Industrial products level nylon 1010 or granulation with thorough drying, stir evenly in kneader with the ratio of above-mentioned different organo montmorillonites according to 100: 5 (weight ratio), when stirring, add whiteruss, extrude through twin screw extruder then, granulation obtains nylon 1010/Nano composite material of montmorillonite.
The performance of prepared organic polynite and sodium-based montmorillonite (Na-Montmorillonite, i.e. MMT) is through TG, DTG and x-ray diffraction experiment analysis, and data see Table 1..
Every performance of table 1. embodiment 1 polynite
The high lattice spacing of embodiment thermal weight loss (%) heat decomposition temperature (nm)
(℃)
OM-01 33.43 254.4，268.0 4.20
OM-02 36.57 451.6 3.50
OM-03 56.09 439.1 3.71
MMT 3.20 -- 1.27
Organo montmorillonite adds in the nylon 1010 matrix and homodisperse, part nylon 1010 molecular chain can insert in the middle of the lamella of layered silicate, the silicate lamella can produce great effect to the crystalline structure of nylon 1010 again conversely, and these structural variations can influence the mechanical property of nylon 1010 to a certain extent.Stretching, bending and impact property to nylon 1010 and Nano composite material of montmorillonite thereof are tested, and obtain that the results are shown in Table 2.
From table data as can be seen, density, tensile strength and the elongation at break of the sample after all fillers are filled all descend to some extent.But the bending strength maximum of PCN-03 nano composite material has improved 24.2% than pure nylon 1010, and modulus in flexure then is 1.6 times of pure nylon 1010.In addition, the bending property of PCN-04 also improves a lot than pure nylon 1010.With regard to shock strength, except that PCN-03 kept substantially, each sample all increased.Wherein the shock strength of PCN-04 is the highest, has improved 6%.
The heat-drawn wire of each sample is that the temperature when Young's modulus decays to 0.9GPa on the dynamic thermomechanical property collection of illustrative plates characterizes.As can be seen, all than pure nylon 1010 height, wherein PCN-04 is the highest for the heat-drawn wire of each sample, has reached 56 ℃, has improved 25 ℃ than pure nylon 1010.
Every performance of table 2. embodiment 1 nylon 1010/Nano composite material of montmorillonite
Performance PCN-01 PCN-02 PCN-03 PCN-04
Polynite type--OM-01 OM-02 OM-03
Polynite content (phr)--3.0 3.0 3.0
Density (g/cm
3) 1.43 1.22 1.24 1.23
Tensile strength (MPa) 70 55 54 53
Elongation at break (%) 383 295 62 154
Flexural strength (MPa) 33 37 41 38
Modulus in flexure (MPa) 521 739 818 771
Notched Izod impact strength (kJ/m
2) 3.33 3.41 3.30 3.52
Heat-drawn wire (℃) 31 55 55 56
Embodiment 2.
With 0.5～20 part of polynite mechanical stirring in the presence of deionized water, form stable suspension, heating in water bath to 50～90 ℃ or at room temperature, add 0.25～10 part of intercalation ion-exchanger and carry out cation exchange reaction, suction filtration, use deionized water washing sediment, unreacted ion-exchanger is removed modified organo montmorillonite;
To mix after 0.5～20 part of above-mentioned modified organo montmorillonite and 100 parts of nylon 1010 monomers grindings; add 5～30 parts of copolymerization constituent monomers, 0.5～5 part of additive, 0.001～1 part of protonating agent and 0.01～20 part of initiator; put into polymeric kettle after mixing; add 1～20 part of dispersion medium again; under CO 2 gas-shielded, be warming up to 190～240 ℃ of polymerizations 4～6 hours, promptly obtain nylon 1010/Nano composite material of montmorillonite.
Every performance of table 3. embodiment 2 nylon 1010s/Nano composite material of montmorillonite
The multiple nylon 1010 of performance nylon 1010/montmorillonite-based nano
Condensation material
Tensile strength (MPa) 48.2 37.1
Tensile modulus (MPa) 464.2 257.9
Elongation at break (%) 329 484
Notched Izod impact strength 16.9 12.0
(kJ/m
2)
Molecular weight (M
η* 10
-4) 1.67 2.49
The mechanical property of nylon 1010/Nano composite material of montmorillonite and nylon 1010 is (as shown in table 3) relatively, and tensile strength has improved 30%; Young's modulus improves 80%; Elongation at break decreases; Shock strength has improved 41%.
Above result shows when polynite content is not high, very strong enhancement is just arranged.This mainly owing to the dispersion of polynite wafer nanoscale and and matrix between strong interfacial interaction.
Claims (13)
1, nylon 1010/Nano composite material of montmorillonite mainly is made up of nylon 1010, polynite, copolymerization constituent monomers, intercalation ion-exchanger, and it is characterized in that: each component according to weight part is
Nylon 1010 monomer 80～110
Copolymerization constituent monomers 0～30
Polynite 0.50～20
Intercalation ion-exchanger 0.25～10
Initiator 0～20
Protonating agent 0～1.0
Additive 0～5
Dispersion medium 0～120
2, according to the described nylon 1010/Nano composite material of montmorillonite of claim 1, it is characterized in that: said polynite is to contain 85～93% polynite silico-aluminate, particle diameter is 200～400 orders, and the disperse phase yardstick is 10～50 nanometers, and cation exchange capacity is 50～200meq/100g.
3,, it is characterized in that said nylon 1010 monomer is a nylon 1010 salt according to the described nylon 1010/Nano composite material of montmorillonite of claim 1.
4,, it is characterized in that said copolymerization constituent monomers is a kind of in hexanolactam, spicy inner formyl amine, laurolactam, the butyrolactam according to the described nylon 1010/Nano composite material of montmorillonite of claim 1.
5, according to the described nylon 1010/montmorillonite composite material of claim 1, it is characterized in that: said intercalation ion-exchanger is one or more in organic amine, pyridines, phenols, alcohols, ester class, amides, carboxylic-acid, anhydrides organic low molecular or the macromolecular compound.
6, according to the described nylon 1010/montmorillonite composite material of claim 5, it is characterized in that: said organic amine is one or more in palmityl trimethyl ammonium chloride, octadecyl trimethyl ammonium chloride, dodecyl benzyl dimethyl ammonium chloride, distearyl dimethyl ammonium chloride, Dodecyl trimethyl ammonium chloride, the brometo de amonio, pyridines is a Polyvinylpyrolidone (PVP), phenols is a meta-cresol, alcohols is a Virahol, the ester class is a n-butyl acetate, amides is a dimethyl formamide, carboxylic-acid is a citric acid, and anhydrides is a maleic anhydride.
7, according to the described nylon 1010/Nano composite material of montmorillonite of claim 1, it is characterized in that: said initiator is 6-aminocaprolc acid or ten diamino acid.
8, according to the described nylon 1010/Nano composite material of montmorillonite of claim 1, it is characterized in that: said protonating agent is a kind of in phosphorous acid, phosphoric acid, hydrochloric acid, sulfuric acid, the acetic acid.
9, according to the described nylon 1010/Nano composite material of montmorillonite of claim 1, it is characterized in that: said additive is 1,6-hexanediamine or dodecyl diamines.
10, according to the described nylon 1010/Nano composite material of montmorillonite of claim 1, it is characterized in that: said dispersion medium is a kind of in water, ethanol, propyl alcohol, the chloroform.
11, prepare the method for the described nylon 1010/Nano composite material of montmorillonite of claim 1, it is characterized in that:
A. with 0.50～20 part of polynite mechanical stirring in deionized water, form stable suspension, heating in water bath to 50～90 ℃ or at room temperature, add 0.25～10 part of intercalation ion-exchanger and carry out cation exchange reaction, suction filtration, use deionized water washing sediment, unreacted ion-exchanger is removed;
B. with a products therefrom heat drying, grind, sieve, add 80～110 parts of nylon 1010 particles, mix, on twin screw extruder, extrude, granulation, promptly get product.
12, prepare the method for claim 1 and 2 described nylon 1010/Nano composite material of montmorillonite, it is characterized in that:
A. with 0.50～20 part of polynite mechanical stirring in deionized water, form stable suspension, heating in water bath to 50～90 ℃ or at room temperature, add 0.25～10 part of intercalation ion-exchanger and carry out cation exchange reaction, suction filtration, use deionized water washing sediment, unreacted ion-exchanger is removed;
B. will mix after 0.5～20 part of a products therefrom and 80～110 parts of nylon 1010 monomers grindings; add 5～30 parts of copolymerization constituent monomers, 0.05～5 part of additive, 0.001～1 part of protonating agent and 0.01～20 part of initiator; put into polymeric kettle after mixing evenly; add 1～120 part of dispersion medium; under CO 2 gas-shielded, be warming up to 190～240 ℃ of polymerizations 4～6 hours, promptly get product.
13,, it is characterized in that cation exchange capacity is 90～110meq/100g according to claim 10 and 11 described nylon 1010/Nano composite material of montmorillonite preparation methods.
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