CN104017359A - Nano-modified nylon material and preparation method thereof - Google Patents
Nano-modified nylon material and preparation method thereof Download PDFInfo
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- CN104017359A CN104017359A CN201410275731.7A CN201410275731A CN104017359A CN 104017359 A CN104017359 A CN 104017359A CN 201410275731 A CN201410275731 A CN 201410275731A CN 104017359 A CN104017359 A CN 104017359A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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Abstract
The invention belongs to the field of high molecular materials and in particular relates to a nanoparticle-modified nylon material and a preparation method thereof. The nanoparticle-modified nylon material is prepared from the following raw materials in parts by weight: 100 parts of a nylon matrix, 2-6 parts of nano silicon carbide, 3-7 parts of nano silicon nitride, 4-10 parts of nano silicon dioxide, 0.3-1 part of aminopropyltriethoxysilane, 5-15 parts of phenolic resin, 3-10 parts of glass fibers and 1-10 parts by volume of a volatilizable solvent which is liquid at normal temperature. The nanoparticle-modified nylon material is remarkably superior to an existing product in tensile strength, compressive strength, notch impact strength, thermal deformation temperature, friction coefficient, heat conductivity and water absorptivity, and is very good in application performance.
Description
Technical field
The invention belongs to polymeric material field, be specifically related to a kind of with nanometer particle-modified nylon material and preparation method thereof.
Background technology
Traditional wear-resistant sheet material is generally metallic substance, and metallic material product in use weares and teares comparatively fast, and work-ing life is short, maintenance load is large; And metallic substance is difficult for carrying out, and embedded peace turns, operational difficulty.Modified plastics is the emphasis of China's new high-tech material development.Modified plastics product not only can reach the strength property of some steel, also has the advantages such as light weight, easily machine-shaping, high tenacity, impact, wearability.Therefore, the trend of " to mould Dai Gang " all displays in a lot of industries at present.
Nylon (PA) claim again polymeric amide, has excellent physical and mechanical properties, has the advantages such as high strength, wear-resisting and chemical resistance simultaneously, thereby be widely used in the fields such as automobile making, electric, mechanical means, space flight and aviation.But the shortcomings such as nylon exists low temperature and dry state impact property is poor, notched Izod impact strength is low.And along with industrial expansion, require also more and more higher to the abrasion resistance properties of nylon parts.At present, the method of improving the wear-resistant frictional behaviour of nylon mainly contains the low macromolecular material of self friction coefficient such as polyethylene that adds tetrafluoroethylene, polyethylene, supra polymer two and carries out modification, or adds the lubricating oil such as silicone oil, mineral oil, alicyclic organic or add the modes such as organic/inorganic fiber or powdery lubricant such as carbon fiber, aramid fiber, molybdenumdisulphide, graphite.
Although these methods have been improved the friction and wear behavior of nylon to a certain extent, often exist a series of shortcomings such as performance ratio, Material Physics intensity are low, materials processing poor performance.And current wear-resistant nylon plate wear resisting property improves, require material to there is high strength, high rigidity, good dimensional stability, the good over-all properties such as toughness and good processibility simultaneously.
Adopt advanced nano modification technology can prepare the new modified plastics of excellent combination property.Are technology for newly-developed with nano-material modified plastics, adopt nano modification can improve scratch-resistant performance, mechanical property, thermal property, flame retardant properties and the barrier property etc. of material.Compared with traditional modifying plastics method, nano material can not only be improved the over-all properties of plastics comprehensively, can also give its unique performance, for modifying plastics provides advanced, effective approach.But, many nano modification technology of reporting in prior art all need nanoparticle to carry out special modification and could effectively improve the performance of nylon material, operation is comparatively complicated, and exist the poor problem of nano material dispersing property in modified matrix, also can affect the modified effect of material.
Summary of the invention
For this reason, technical problem to be solved by this invention is available technology adopting nanotechnology modified nylon materials complicated operation and the undesirable problem of effect, and then a kind of nano modification nylon material with high strength, high rigidity, good dimensional stability and good toughness is provided.
For solving the problems of the technologies described above, nano modification nylon material of the present invention, is prepared from by following raw material: under nylon matrix 100 weight parts, nanometer silicon carbide 2-6 weight part, nano-silicon nitride 3-7 weight part, nano silicon 4-10 weight part, amine propyl-triethoxysilicane 0.3-1 weight part, resol 5-15 weight part, glass fibre 3-10 weight part and normal temperature, be liquid volatilizable solvent 1-10 parts by volume;
The relation that described weight part is g/mL in parts by volume.
Preferably, described nano modification nylon material, is prepared from by following raw material: under nylon matrix 100 weight parts, nanometer silicon carbide 3-5 weight part, nano-silicon nitride 4-6 weight part, nano silicon 6-9 weight part, amine propyl-triethoxysilicane 0.5-0.8 weight part, resol 7-12 weight part, glass fibre 5-8 weight part and normal temperature, be liquid solvent flashing 3-8 parts by volume.
Optimum, described nano modification nylon material, is prepared from by following raw material: under nylon matrix 100 weight parts, nanometer silicon carbide 4 weight parts, nano-silicon nitride 5 weight parts, nano silicon 7 weight parts, amine propyl-triethoxysilicane 0.6 weight part, resol 10 weight parts, glass fibre 7 weight parts and normal temperature, be liquid volatilizable solvent 5 parts by volume.
Nylon 6, nylon 12 and nylon 66 that described nylon matrix is 1-3: 2-4: 4-6 by weight ratio form.
Preferably, the weight ratio of described nylon 6, nylon 12 and nylon 66 is 2: 3: 5.
Under described normal temperature, be selected from hydro carbons for liquid solvent flashing.
The invention also discloses a kind of method of preparing above-mentioned nano modification nylon material, comprise the steps:
(1) get described nanometer silicon carbide, nano-silicon nitride, nano silicon according to selected parts by weight and mix, be added in the solvent flashing of selected parts by volume, mix for subsequent use;
(2) get described nylon matrix, amine propyl-triethoxysilicane, resol and glass fibre according to selected parts by weight and mix, and be heated to 40-50 DEG C of reaction 1-2h; Be warming up to 100-120 DEG C in the mode of gradient increased temperature subsequently, and continue reaction 2-3h;
(3) the reacted mixture of step (2) is cooled to after room temperature, be added in the solvent mixing in step (1) and mix, and will mix material and add in twin screw extruder, at 200-220 DEG C through extruding, cooling, granulation, to obtain final product.
In described step (2), described gradient increased temperature mode refers in the mode of 15-20 DEG C/gradient and heats up, and completes intensification in the initial 2-3min that starts heating schedule, and maintains sustained reaction 1-1.5 hour at this temperature.
The invention also discloses a kind of nano modification nylon material preparing according to aforesaid method.
Technique scheme of the present invention has the following advantages compared to existing technology:
1, nano modification nylon material of the present invention, utilize the nanoparticle of screening meticulously to cooperatively interact, described nylon material is carried out to modification, and be aided with the cooperation of the material such as resol and glass fibre, no matter preparation-obtained nylon material is that tensile strength, compressive strength, breach electuary intensity, heat-drawn wire or frictional coefficient, thermal conductivity and water-intake rate are all obviously better than currently available products, has fabulous application performance;
2, material of the present invention, utilizes described nanoparticle is scattered in volatilizable solvent, and utilize its volatile performance, makes fabulous being scattered in described nylon material of nanoparticle, has further strengthened the effect of modification;
3, preparation method of the present invention, utilizes the form of gradient increased temperature, has further promoted raw-material modification performance, and obtained product performance are superior.
Embodiment
Embodiment 1
Nano modification nylon material described in the present embodiment, is prepared from by following raw material:
Under nylon matrix 100kg, nanometer silicon carbide 2kg, nano-silicon nitride 7kg, nano silicon 4kg, amine propyl-triethoxysilicane 1kg, resol 5kg, glass fibre 10kg and normal temperature, be liquid volatilizable solvent 1L.
The method of preparing nano modification nylon material described in the present embodiment, comprises the steps:
(1) get described nanometer silicon carbide, nano-silicon nitride, nano silicon according to selected weight and mix, be added in the solvent flashing of selected volume, mix for subsequent use;
(2) get described nylon matrix, amine propyl-triethoxysilicane, resol and glass fibre according to selected parts by weight and mix, and be heated to 40 DEG C of reaction 1-2h; Carry out gradient increased temperature program taking the temperature difference of 15 DEG C as a gradient subsequently, be specially at 2-3min temperature is raise 15 DEG C, and maintain sustained reaction 1-1.5 hour at this temperature; By that analogy, until system is warming up to 100 DEG C, and continue reaction 2-3h;
(3) the reacted mixture of step (2) is cooled to after room temperature, be added in the solvent mixing in step (1) and mix, and will mix material and add in twin screw extruder, at 200-220 DEG C through extruding, cooling, granulation, to obtain final product.
Embodiment 2
Nano modification nylon material described in the present embodiment, is prepared from by following raw material:
Under nylon matrix 100kg, nanometer silicon carbide 6kg, nano-silicon nitride 3kg, nano silicon 10kg, amine propyl-triethoxysilicane 0.3kg, resol 15kg, glass fibre 3kg and normal temperature, be liquid volatilizable solvent 10L.
The method of preparing nano modification nylon material described in the present embodiment, comprises the steps:
(1) get described nanometer silicon carbide, nano-silicon nitride, nano silicon according to selected weight and mix, be added in the solvent flashing of selected volume, mix for subsequent use;
(2) get described nylon matrix, amine propyl-triethoxysilicane, resol and glass fibre according to selected parts by weight and mix, and be heated to 40 DEG C of reaction 2h; Carry out gradient increased temperature program taking the temperature difference of 20 DEG C as a gradient subsequently, be specially at 2-3min temperature is raise 20 DEG C, and maintain at this temperature sustained reaction 1 hour; By that analogy, until system is warming up to 120 DEG C, and continue reaction 3h;
(3) the reacted mixture of step (2) is cooled to after room temperature, be added in the solvent mixing in step (1) and mix, and will mix material and add in twin screw extruder, at 200-220 DEG C through extruding, cooling, granulation, to obtain final product.
Embodiment 3
Nano modification nylon material described in the present embodiment, is prepared from by following raw material:
Under nylon matrix 100kg, nanometer silicon carbide 3kg, nano-silicon nitride 6kg, nano silicon 6kg, amine propyl-triethoxysilicane 0.8kg, resol 7kg, glass fibre 8kg and normal temperature, be liquid solvent flashing 3L.
The method of preparing nano modification nylon material described in the present embodiment, comprises the steps:
(1) get described nanometer silicon carbide, nano-silicon nitride, nano silicon according to selected weight and mix, be added in the solvent flashing of selected volume, mix for subsequent use;
(2) get described nylon matrix, amine propyl-triethoxysilicane, resol and glass fibre according to selected parts by weight and mix, and be heated to 50 DEG C of reaction 1h; Carry out gradient increased temperature program taking the temperature difference of 15 DEG C as a gradient subsequently, be specially at 2-3min temperature is raise 15 DEG C, and maintain at this temperature sustained reaction 1 hour; By that analogy, until system is warming up to 110 DEG C, and continue reaction 2-3h;
(3) the reacted mixture of step (2) is cooled to after room temperature, be added in the solvent mixing in step (1) and mix, and will mix material and add in twin screw extruder, at 200-220 DEG C through extruding, cooling, granulation, to obtain final product.
Embodiment 4
Nano modification nylon material described in the present embodiment, is prepared from by following raw material:
Under nylon matrix 100kg, nanometer silicon carbide 5kg, nano-silicon nitride 4kg, nano silicon 9kg, amine propyl-triethoxysilicane 0.5kg, resol 12kg, glass fibre 5kg and normal temperature, be liquid solvent flashing 8L.
The method of preparing nano modification nylon material described in the present embodiment, comprises the steps:
(1) get described nanometer silicon carbide, nano-silicon nitride, nano silicon according to selected weight and mix, be added in the solvent flashing of selected volume, mix for subsequent use;
(2) get described nylon matrix, amine propyl-triethoxysilicane, resol and glass fibre according to selected parts by weight and mix, and be heated to 50 DEG C of reaction 1-2h; Carry out gradient increased temperature program taking the temperature difference of 20 DEG C as a gradient subsequently, be specially at 2-3min temperature is raise 20 DEG C, and maintain at this temperature sustained reaction 1 hour; By that analogy, until system is warming up to 110 DEG C, and continue reaction 2-3h;
(3) the reacted mixture of step (2) is cooled to after room temperature, be added in the solvent mixing in step (1) and mix, and will mix material and add in twin screw extruder, at 200-220 DEG C through extruding, cooling, granulation, to obtain final product.
Embodiment 5
Nano modification nylon material described in the present embodiment, is prepared from by following raw material:
Under nylon matrix 100kg, nanometer silicon carbide 4kg, nano-silicon nitride 5kg, nano silicon 7kg, amine propyl-triethoxysilicane 0.6kg, resol 10kg, glass fibre 7kg and normal temperature, be liquid volatilizable solvent 5L.
The method of preparing nano modification nylon material described in the present embodiment, comprises the steps:
(1) get described nanometer silicon carbide, nano-silicon nitride, nano silicon according to selected weight and mix, be added in the solvent flashing of selected volume, mix for subsequent use;
(2) get described nylon matrix, amine propyl-triethoxysilicane, resol and glass fibre according to selected parts by weight and mix, and be heated to 45 DEG C of reaction 1-2h; Carry out gradient increased temperature program taking the temperature difference of 18 DEG C as a gradient subsequently, be specially at 2-3min temperature is raise 18 DEG C, and maintain at this temperature sustained reaction 1.5 hours; By that analogy, until system is warming up to 117 DEG C, and continue reaction 2h;
(3) the reacted mixture of step (2) is cooled to after room temperature, be added in the solvent mixing in step (1) and mix, and will mix material and add in twin screw extruder, at 200-220 DEG C through extruding, cooling, granulation, to obtain final product.
Effect example
The modified nylon materials that above-described embodiment 1-5 is made carries out testing performance index, and concrete test data refers to following table.
No matter nano modification nylon material of the present invention is that tensile strength, compressive strength, breach electuary intensity, heat-drawn wire or frictional coefficient, thermal conductivity and water-intake rate are all obviously better than currently available products, has fabulous application performance.
Obviously, above-described embodiment is only for example is clearly described, and the not restriction to embodiment.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here without also giving exhaustive to all embodiments.And the apparent variation of being extended out thus or variation are still among the protection domain in the invention.
Claims (9)
1. a nano modification nylon material, it is characterized in that, be prepared from by following raw material: under nylon matrix 100 weight parts, nanometer silicon carbide 2-6 weight part, nano-silicon nitride 3-7 weight part, nano silicon 4-10 weight part, amine propyl-triethoxysilicane 0.3-1 weight part, resol 5-15 weight part, glass fibre 3-10 weight part and normal temperature, be liquid volatilizable solvent 1-10 parts by volume;
The relation that described weight part is g/mL in parts by volume.
2. nano modification nylon material according to claim 1, it is characterized in that, be prepared from by following raw material: under nylon matrix 100 weight parts, nanometer silicon carbide 3-5 weight part, nano-silicon nitride 4-6 weight part, nano silicon 6-9 weight part, amine propyl-triethoxysilicane 0.5-0.8 weight part, resol 7-12 weight part, glass fibre 5-8 weight part and normal temperature, be liquid solvent flashing 3-8 parts by volume.
3. nano modification nylon material according to claim 1 and 2, it is characterized in that, be prepared from by following raw material: under nylon matrix 100 weight parts, nanometer silicon carbide 4 weight parts, nano-silicon nitride 5 weight parts, nano silicon 7 weight parts, amine propyl-triethoxysilicane 0.6 weight part, resol 10 weight parts, glass fibre 7 weight parts and normal temperature, be liquid volatilizable solvent 5 parts by volume.
4. according to the arbitrary described nano modification nylon material of claim 1-3, it is characterized in that, nylon 6, nylon 12 and nylon 66 that described nylon matrix is 1-3: 2-4: 4-6 by weight ratio form.
5. nano modification nylon material according to claim 4, is characterized in that, the weight ratio of described nylon 6, nylon 12 and nylon 66 is 2: 3: 5.
6. according to the arbitrary described nano modification nylon material of claim 1-5, it is characterized in that, under described normal temperature, be selected from hydro carbons for liquid solvent flashing.
7. a method of preparing the arbitrary described nano modification nylon material of claim 1-6, is characterized in that, comprises the steps:
(1) get described nanometer silicon carbide, nano-silicon nitride, nano silicon according to selected parts by weight and mix, be added in the solvent flashing of selected parts by volume, mix for subsequent use;
(2) get described nylon matrix, amine propyl-triethoxysilicane, resol and glass fibre according to selected parts by weight and mix, and be heated to 40-50 DEG C of reaction 1-2h; Be warming up to 100-120 DEG C in the mode of gradient increased temperature subsequently, and continue reaction 2-3h;
(3) the reacted mixture of step (2) is cooled to after room temperature, be added in the solvent mixing in step (1) and mix, and will mix material and add in twin screw extruder, at 200-220 DEG C through extruding, cooling, granulation, to obtain final product.
8. preparation method according to claim 7, it is characterized in that, in described step (2), described gradient increased temperature mode refers in the mode of 15-20 DEG C/gradient and heats up, and complete intensification in the initial 2-3min that starts heating schedule, and maintain sustained reaction 1-1.5 hour at this temperature.
9. the nano modification nylon material preparing according to method described in claim 7 or 8.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104774453A (en) * | 2015-04-22 | 2015-07-15 | 合肥康龄养生科技有限公司 | Reinforced nylon composite material and preparation method thereof |
| CN105086438A (en) * | 2015-08-03 | 2015-11-25 | 来安县隆华摩擦材料有限公司 | Phenolic resin automobile clutch friction material and preparation method thereof |
| CN111888978A (en) * | 2020-06-23 | 2020-11-06 | 江苏弘盛新材料股份有限公司 | Raw material mixing device and process for hygroscopic improved nylon 6 |
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| CN104774453A (en) * | 2015-04-22 | 2015-07-15 | 合肥康龄养生科技有限公司 | Reinforced nylon composite material and preparation method thereof |
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| CN111888978A (en) * | 2020-06-23 | 2020-11-06 | 江苏弘盛新材料股份有限公司 | Raw material mixing device and process for hygroscopic improved nylon 6 |
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