CN1206028A - Nanometer composite polyamide-clay material and its preparation - Google Patents
Nanometer composite polyamide-clay material and its preparation Download PDFInfo
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- CN1206028A CN1206028A CN 97112237 CN97112237A CN1206028A CN 1206028 A CN1206028 A CN 1206028A CN 97112237 CN97112237 CN 97112237 CN 97112237 A CN97112237 A CN 97112237A CN 1206028 A CN1206028 A CN 1206028A
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- clay
- polymeric amide
- intercalation
- soil
- nylon
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Abstract
Clay and polyamide after intercalation treatment are molten, mixed and extruded in screw extruder, and through mechanical and chemical effect inside limited space clay and polyamide are combined and dispersed in nanometer size to prepare the high-performance nanometer composite material. The present invention is simple, uses no solvent and post-treatment, has low cost and can reach the effect of intercalation polymerization.
Description
The present invention relates to a kind of polymeric amide (nylon) matrix material, specially refer to the matrix material that polymeric amide and inorganic materials are formed.
Nylon is a kind of engineering plastics of widespread use, has good physics, mechanical property, but since the existence of amide group, the water-intake rate height of nylon, heat-drawn wire is low, and modulus is low, has limited its application.Usually adopt filling-modified method to improve its dimensional stability and raising rigidity, but cause particularly impelling strength decline of the strength of materials.The preparation nano composite material is filling-modified new way.Because nanoscale effect and strong interfacial interaction make nano composite material have excellent mechanical property, thermotolerance and good processing properties.
Chinese patent CN1138593A discloses a kind of intercalation polymeric and has prepared the nanometer composite polyamide-clay material method.The above-mentioned patent preparation process that is known as " single stage method " is, the intercalation expansionization processing of clay is once finished with processing back clay and being aggregated in the reactor of monomer of polyamide, clay of laminar silicate is combined and with the nanoscale homodisperse by Coulomb's force and covalent linkage with polyamide substrate, thereby obtain the nanometer composite polyamide-clay material of tool excellent properties.The shortcoming of above-mentioned patent is that the intercalation polymeric process needs the large quantity of moisture dispersion media with monomer and intercalation soil homodisperse, needs again the water underpressure distillation is removed before polymerization, carry out smoothly to guarantee reaction, so energy consumption is big, and needs production unit is done corresponding improvement.So intercalation polymeric mainly is applicable to the production in enormous quantities of fixing prescription, is unsuitable for many kinds, small serial production.
In order to adapt to the many kinds of market demand, the actual requirement of small serial production the invention provides a kind of melt intercalation preparation and has high performance nanometer composite polyamide-clay material and preparation method thereof.
The melt intercalation is directly macromolecular chain to be inserted between the accurate two-dimentional silicate clay lamella and it is dissociated, and obtains high molecular polymer/clay nanocomposites.Rigidity, the thermotolerance of inorganics are combined on nanoscale with toughness, the workability of polymkeric substance, and the composite property of preparation surpasses the material of traditional blending and modifying significantly, and suitable with the performance of composites of intercalation polymeric.
Nanometer composite polyamide-clay material raw material of the present invention comprises following component and content (weight part):
Polymeric amide 100
Intercalation soil 1-50
Additive 0.05-5
The used polymeric amide of the present invention is nylon 6, nylon 66, nylon 12, NYLON610 etc.The present invention can use the above-mentioned polymeric amide of technical grade as raw material.
The intercalation soil that the present invention uses is a kind of clay through the processing of intercalation expansionization.The intercalation mount is drawn together following component and content (weight part):
Clay 1-50
Intercalator 0.4-20
Protonating agent 0.01-1.0
Clay provided by the present invention is that a class mineral major ingredient is for containing the layered silicate of 85-93% polynite (Mont).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 the unit cell surface-area is 2 * 5.15 * 8.9A
2, the heavy 700-800g/mol of structure cell.Montmorillonite clay layer internal surface has negative charge, each negative charge footprint area 25-200A
2, specific surface area 700-800m
2/ g.Interlayer cation Na
+, Ca
2+, Mg
2+Deng being the interchangeability negatively charged ion, after the organic ammonium salt exchange, can make macromolecular chain be inserted into interlayer.Clay mineral has cationic exchange total volume (CEC) 50-200meq/100g.
The clay particle diameter is generally 40-70 μ m, and lamellar spacing is 9.6 , and interfloor distance is 2-5 , and the interfloor distance of intercalation soil is increased to 15-20 .The clay layer spacing is increased to 30-50 behind the melt intercalation, and the clay layer spacing is bigger, and performance of composites better.
Clay content is 1-50 (weight part) in the present invention, and when content is lower than 1 part, clay is not enough to produce enough enhancements and thermotolerance, and when content surpasses 50 parts, material is difficult to extruding pelletization.In the present invention, the clay optimum content is 3-20 part.
The intercalator that the present invention adopts is long chain alkyl ammonium salt, nylon salt, 6-aminocaprolc acid, ten diamino acid etc.
Protonating agent of the present invention can be protonic acids such as sulfuric acid, phosphoric acid, hydrochloric acid, sulfonic acid, acetic acid.
The additive that the present invention adopts is lubricant, oxidation inhibitor, toughner, nucleator etc., its effect is the consistency of improving between mineral filler and the organic polymer matrix, the crystal habit of control resin is with toughness, the rigidity of improving matrix material and further reduce spherulite size, improve the transparency of matrix material, improve working (machining) efficiency.Lubricant can be white oil, Ployethylene Wax etc.Oxidation inhibitor can be antioxidant 264, antioxidant CA, antioxidant 1010 etc.Additive can separately or be used.
Nanometer composite polyamide-clay material preparation method of the present invention is undertaken by following step:
(1) is clay 1-50 part high-speed stirring in the presence of the water dispersion medium of 20-800 part of 50-200meq/100g with the cationic exchange total volume, forms the stable suspersion system.
(2) intercalator 0.4-20 part is stirred the protonated solution of formation in the presence of water dispersion medium 5-200 part and protonating agent 0.01-1 part, be injected in the above-mentioned slurry.
(3) with above-mentioned mixed solution 60-100 ℃ of following high-speed stirring 3h after-filtration drying, obtain intercalation soil through pulverizing.
(4) then 100 parts of polymeric amide and additive 0.05-1 part were stirred 5-10 minute in high speed kneader high speed, add intercalation soil 1-50 part again and make it to mix the back and under 190 ℃-250 ℃, extrude with twin screw extruder, can discharging standby.
This matrix material can be 210 ℃-240 ℃ in injection temperature, and injection pressure is injection molding under the processing conditions of 60-120MPa.Twin screw rotating speed, screw configuration are filled compound identical with routine.
Melt intercalation technique provided by the invention is at first intercalator to be inserted into accurate two-dimentional silicate clay sheet of material chien shih clay layer to strut, and then rely on macromolecular chain macromolecular chain to be inserted into the silicate plate interlayer and lamella is dissociated with the shearing force of interaction between the intercalator organic group and screw rod, make clay reach the homodisperse of nanoscale, form high molecular polymer/clay nanocomposites.Compare with the intercalation polymeric method, weak point consuming time, simple to operate, the efficient height is easy to industrial applications, and performance is suitable with in-situ inserted polymeric material.
The clay dispersion phase yardstick of melt intercalation composite material of the present invention is 20-50nm, reaches the dispersion of nanoscale, has formed polymer based nanocomposites.Between polymeric matrix and inorganic disperse phase very strong interaction is arranged, fully that the high strength of inorganics, high heat resistance and polymer is good toughness, workability combine, and have obtained the matrix material of excellent performance.
Polyamides provided by the invention west amine/clay nanocomposites, its reinforcing effect surpasses the prepared matrix material of traditional blending technology, and especially thermotolerance is improved largely, and impelling strength do not descend, and over-all properties is suitable with in-situ inserted polymer composite material.Big reinforcing effect can think clay layer nanoscale in polymeric matrix dispersion and and polymeric matrix between strong interfacial interaction.
Embodiment 1.
With the cationic exchange total volume is the clay 10g of 100meq/100g, adds water 800g, and high-speed stirring is 0.5 hour after waiting to be uniformly dispersed, and obtains slurry A.In concentrated hydrochloric acid 1g and 5g cetyltrimethyl ammonium, add water 200g, be warming up to 60-100 ℃ of stirring, until forming even protonated solution B.Be incubated 60-100 ℃, the B drop is added in the A liquid, high-speed stirring 3 hours, cold filtration, washing, drying, mechanical disintegration, vacuum-drying obtain intercalation soil.Then 1000g polymeric amide and 1g white oil or Ployethylene Wax were stirred 5 minutes in high speed kneader high speed, add intercalation soil 10g again and stir after 5 minutes and extrude on forcing machine, each section of forcing machine temperature is: 200,240 ℃, and 240 ℃, 220 ℃.Injection molding on injector behind the granulating and drying, its each section of injector temperature is: 1 section is 180 ℃, and 2 sections is 220 ℃, and 3 sections is 220 ℃, and nozzle is 210 ℃, injection pressure is 80MPa.Measure the d of material medium clay soil through the X-ray diffraction
001The interplanar distance of face diffraction peak and transmission electron microscope observation clay layer thickness shows that clay is strutted even dissociated, and lamellar spacing only is 20-50nm, and clay is dispersed in the polyamide substrate with nanoscale, and mechanical property sees Table 1.
Table 1
| Embodiment | Clay content (gram) | Caprolactam content (gram) | ?d 001Interplanar distance (A) | Tensile strength (MPa) | Tensile modulus (GPa) | Shock strength (J/M) | Heat-drawn wire (℃, 18.6 Kg/cm 2) |
| ?1 | ?1O | ?1000 | ?＞100 | ?93 | ?3.5 | ?34 | ?82 |
| ?2 | ?30 | ?1000 | ?＞100 | ?86 | ?4.0 | ?26 | ?96 |
| ?3 | ?45 | ?1000 | ?＞100 | ?92 | ?4.1 | ?26 | ?112 |
| ?4 | ?70 | ?1000 | ?＞100 | ?86 | ?4.3 | ?33 | ?118 |
| ?5 | ?110 | ?1000 | ?40 | ?90 | ?5.7 | ?24 | ?127 |
| ?6 | ?250 | ?1000 | ?25 | ?96 | ?6.3 | ?26 | ?136 |
| ?7 | ?500 | ?1000 | ?25 | ?/ | ?/ | ?/ | ?/ |
Embodiment 2-7.
With example 1, wherein clay content is respectively 30g, 42g, 70g, 110g, 250g, 500g.Its mechanical property sees Table 1.
Claims (8)
1. polymeric amide clay nanocomposites is characterized in that described nanometer composite polyamide-clay material raw material comprises following component and content (weight part):
Polymeric amide 100
Intercalation soil 1-50
Additive 0.05-5
Described matrix material medium clay soil disperse phase yardstick is 20-50nm, and described intercalation soil is the clay through the processing of intercalation expansionization.
2. according to the described a kind of polymeric amide clay nanocomposites of claim 1, it is characterized in that the intercalation mount draws together following component and content: (weight part)
Clay 1-50
Intercalator 0.4-20
Protonating agent 0.01-1.0
Described raw clay is the aluminosilicate that contains the 85-93% polynite, and particle diameter is 40-70 μ m, and cation exchange capacity is 50-200meq/100g, and clay layer thickness is 9.6 , and the clay seam spacing is 2-5 , and intercalation soil sheet interlayer spacing is 15-20 .
3. according to the described a kind of polymeric amide clay nanocomposites of claim l, it is characterized in that described polyamide substrate is nylon 6, nylon 66, nylon 12 or NYLON610.
4。A kind of polymeric amide clay nanocomposites according to claim 1 is characterized in that described intercalator is long chain alkyl ammonium salt, nylon salt, 6-aminocaprolc acid or ten diamino acid.
5. a kind of polymeric amide clay nanocomposites according to claim 1 is characterized in that described protonating agent is a hydrochloric acid.
6. a kind of polymeric amide clay nanocomposites according to claim 1 is characterized in that described additive is white oil or Ployethylene Wax.
7. a kind of polymeric amide clay nanocomposites according to claim 1 is characterized in that described additive is antioxidant 264, antioxidant CA or antioxidant 1010.
8. a kind of polymeric amide clay nanocomposites according to claim 1 and preparation method thereof is characterized in that being undertaken by following step:
(1) with the cationic exchange total volume is clay 1-50 part high-speed stirring in the presence of 20-800 part water dispersion medium of 50-200meq/100g, forms the stable suspersion system.
(2) intercalator 0.4-20 part is stirred the protonated solution of formation in the presence of dispersion medium 5-200 part and protonating agent 0.01-1 part, is injected into then in the above-mentioned slurry,
(3) with above-mentioned mixed solution at 60-100 ℃ of following high-speed stirring 3h, obtain intercalation soil through pulverizing,
(4) with 100 parts of polymeric amide and 0.05-1 part white oil or Ployethylene Wax after high speed kneader high speed stirs 5-10 minute, adding intercalation soil 1-50 part makes it to mix, then under 190 ℃ of-240 ℃ of temperature with the twin screw extruder extruding pelletization, can discharging standby
(5) injection temperature is 210 ℃-240 ℃, and injection pressure is 60-120MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97112237A CN1081207C (en) | 1997-07-17 | 1997-07-17 | Nanometer composite polyamide-clay material and its preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97112237A CN1081207C (en) | 1997-07-17 | 1997-07-17 | Nanometer composite polyamide-clay material and its preparation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1206028A true CN1206028A (en) | 1999-01-27 |
| CN1081207C CN1081207C (en) | 2002-03-20 |
Family
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97112237A Expired - Fee Related CN1081207C (en) | 1997-07-17 | 1997-07-17 | Nanometer composite polyamide-clay material and its preparation |
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| CN1101415C (en) * | 2000-01-05 | 2003-02-12 | 浙江大学 | Preparation of composite nanometer polyimide/clay film with very low thermal expansion coefficient |
| CN1107092C (en) * | 2000-10-20 | 2003-04-30 | 中国科学院化学研究所 | Polyamide 66 composite material and prepn. method therefor |
| CN1314730C (en) * | 2005-04-28 | 2007-05-09 | 华东理工大学 | Polyamide extruded from reaction between low dimensional nano clay and monomer of polyamide, and preparation method thereof |
| CN100395288C (en) * | 2004-12-27 | 2008-06-18 | 上海杰事杰新材料股份有限公司 | Fuel tank made from Nano composite material of nylon / clay, and preparation method |
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| US4739007A (en) * | 1985-09-30 | 1988-04-19 | Kabushiki Kaisha Toyota Chou Kenkyusho | Composite material and process for manufacturing same |
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| NL1012974C2 (en) * | 1999-09-03 | 2001-03-06 | Dsm Nv | Extruded nanocomposite molded part, comprising at least a polycondensate and a nanofiller, as well as a process for their preparation. |
| CN1101415C (en) * | 2000-01-05 | 2003-02-12 | 浙江大学 | Preparation of composite nanometer polyimide/clay film with very low thermal expansion coefficient |
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