CN104098890A - HPN (high temperature resistant nylon)/(thermotropic liquid crystal polymer) / HNTs (halloysite nanotubes) composite material and preparation method thereof - Google Patents
HPN (high temperature resistant nylon)/(thermotropic liquid crystal polymer) / HNTs (halloysite nanotubes) composite material and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of engineering plastics, and relates to a HPN (high temperature resistant nylon) / TLCP (thermotropic liquid crystal polymer) / HNTs (halloysite nanotubes) composite nano material and a preparation method thereof. The material comprises the following components by weight: 70-80 parts of semi aromatic nylon, 5-15 parts of thermotropic liquid crystal polymer, 10-20 parts of halloysite nanotubes, 0.2-0.5 part of a compatible agent, 0.3-1 part of a lubricant and 0.5-0.2 part of an antioxidant. Compared with the prior art, the HNTs can be well compatible with the high temperature resistant nylon, and is good in self dispersivity and not easy to agglomerate, so that the HPN/TLCP/HNTs composite material with high strength, high rigidity, heat resistance and excellent chemical stability performance can be obtained, the HPN/TLCP/HNTs composite material is added with HNTs relatively cheap in price, and avoids the disadvantage of too high use cost caused by single use of the high temperature resistant nylon and the TLCP, and the preparation method is simple in process.
Description
Technical field
The invention belongs to engineering plastics technical field, relate to a kind of semi-aromatic nylon/TLCP/halloysite nanotubes (HPN/TLCP/HNTs) matrix material and preparation method thereof.
Background technology
Nearly decades, nylon is in industry and in lifely had a significant progress.Being widely used but recent years is due to electric industrial expansion, the surface mounted technology of SMT(especially), makes to material is high temperature resistant, to wait the requirement of properties more and more higher in industry.And high temperature resistant nylon relies on its high-melting-point, good mechanical property opens gradually a slice world in industry now.
At present maximum high temperature resistant nylon used is DSM(DSM) PA46, but because PA46 is aliphatics nylon, in high temperature resistant and mechanical properties still not as good as aromatic series or semi-aromatic nylon.Therefore, as PA6T, PA9T, PA10T semi-aromatic nylon, obtained very large development.But the poor fluidity of high temperature resistant nylon, that processing characteristics is bad, mechanical property can not meet the shortcomings such as industrial requirements is day by day obvious, therefore seek a kind of mechanical property, processing characteristics, flowing property all excellent high temperature resistant nylon seem particularly important.TLCP (TLCP) has good mechanical property, at many high-technology fields, is widely used.Liquid crystalline polymers
not onlyhave high strength, the mechanical property of high-modulus, also has good thermostability and mobility, thermotolerance and chemical proofing, and wear-resisting, anti-attrition is all excellent.Weathering resistance, the radiation resistance of TLCP are good, have excellent flame retardant resistance, can knock down the flame and no longer proceed burning.Its burning grade reaches UL94V-0 level level.
Halloysite (HNTs) is a kind of natural nanotube-shaped material of many walls, silicon-oxy tetrahedron and alumina octahedral, consists of, and belongs to kaolinite class.Because HNTs outer wall contains certain hydroxyl, there is polarity, can form hydrogen bond with high temperature resistant nylon, and between HNTs, interaction force is not strong, be easy to disperse.Therefore, HNTs adds the over-all properties that can improve HPN/TLCP/HNTs matrix material, reduces costs.
The invention provides the HPN/TLCP/HNTs matrix material of a kind of high strength, high rigidity, resistance toheat and chemical stability excellence, in matrix material, semi-aromatic nylon and liquid crystalline polymers make up for each other's deficiencies and learn from each other, both toughness and the crystallization rate of semi-aromatic nylon had been improved, improved again intensity and the rigidity of liquid crystalline polymers, HNTs nano-tube material add can reinforced composite mechanical property; Thereby prepared matrix material has good over-all properties.And the HPN/TLCP/HNTs matrix material that the present invention makes, when having superstrength, keeps the physical and mechanical property of semi-aromatic nylon, original other the every excellences of liquid crystal polymer material.
Summary of the invention
The object of the invention is to provides a kind of semi-aromatic nylon/TLCP/halloysite nanotubes (HPN/TLCP/HNTs) matrix material and preparation method thereof for overcoming the defect of prior art.
For achieving the above object, the present invention is by the following technical solutions:
Semi-aromatic nylon/TLCP/halloysite nanotubes (HPN/TLCP/HNTs) matrix material, by the component that comprises following weight part, made:
Semi-aromatic nylon (HPN) 70-80 part,
TLCP (TLCP) 5-15 part,
Halloysite nanotubes (HNTs) 10-20 part,
Compatilizer 0.2-0.5 part,
Lubricant 0.3-1.0 part,
Oxidation inhibitor 0.2-0.5 part.
Described semi-aromatic nylon is selected from one or more in PA6T, PA7T, PA8T, PA9T, PA10T or PA12T, is preferably one or more in PA9T, PA10T or PA12T.
Described liquid crystalline polymers comprises all aromatic TLCP or semi-aromatic TLCP.TLCP mainly by P-hydroxybenzoic acid (HBA), Resorcinol (HQ), mix aromatic diacid (MA), m-phthalic acid (IA), terephthalic acid (TA), 4.4 '-dicarboxyl-N-phenylbenzamaide (NA), 4.4 '-phenyl ether dioctyl phthalate, biphenyl, polymkeric substance that the repeating unit of drawing containing naphthalene nucleus polymkeric substance etc. forms, the preferred 5130L of Du Pont or Polyplastics E130i etc.
The diameter of described halloysite nanotubes (HNTs) is 50～100 μ m.
Described compatilizer is can interactional polyfunctional compound with liquid crystalline polymers and semi-aromatic nylon resin or both, is physical property compatilizer or chemical solubilizing agent; Further be selected from one or more in toxilic acid, maleic anhydride, fumaric acid, methylene-succinic acid or glycidyl acrylate; Be preferably one or more in maleic anhydride or toxilic acid.
Described lubricant comprises one or more in internal lubricant or external lubricant.
Described internal lubricant is fatty acid amide series lubricant agent or hydro carbons lubricant, and wherein fatty acid amide series lubricant agent is N, N '-bis-ethylene hard fatty acids acid amides, stearic amide or amine hydroxybenzene; Described hydro carbons lubricant is paraffin, polyethylene wax or Poly Propylene Wax.
Described external lubricant is nonpolar lubricant, and described nonpolar lubricant is siloxanes, silicon-dioxide or diatomite etc.
Described oxidation inhibitor is phenols high-temperature antioxidant, is selected from four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, β-(3,5-di-tert-butyl-hydroxy phenyl) the positive octadecanol ester of propionic acid or 1,3,5-tri-(the 4-tertiary butyl-3-hydroxyl-2,6-dimethyl benzyl)-1,3,5-triazine-2,4,6-(1H, 3H, 5H) one or more in-triketone.
A preparation method for above-mentioned HPN/TLCP/HNTs matrix material, comprises the following steps:
(1) first that high temperature resistant nylon resin, liquid crystalline polymers, halloysite nanotubes is dry respectively;
(2) lubricant, processing aid and compatilizer are mixed, dry;
(3) raw material of step (1), (2) being handled well mixes;
(4) raw material mixing in step (3) is melt extruded to granulation through twin screw extruder.
In described step (1), semi-aromatic nylon resin, liquid crystalline polymers and halloysite nanotubes were respectively at 120～130 ℃, 140～150 ℃ and 90～100 ℃ of forced air dryings 8～10 hours;
In described step (2), utilize homogenizer to carry out, after high-speed mixing, putting into loft drier and being dried to lubricant, oxidation inhibitor and compatilizer, drying temperature is 90～100 ℃, and be 1～3 hour time of drying;
In described step (3), mixing time is 5～10min.
In described step (4), each of twin screw extruder section Temperature Setting is: 275 ± 10 ℃ of district's temperature, two 275 ± 10 ℃ of district's temperature, three 280 ± 10 ℃ of district's temperature, four 285 ± 10 ℃ of district's temperature, five 295 ± 10 ℃ of district's temperature, six 295 ± 10 ℃ of district's temperature, seven 295 ± 10 ℃ of district's temperature, eight 290 ± 10 ℃ of district's temperature, nine 285 ± 10 ℃ of district's temperature, ten 285 ± 10 ℃ of district's temperature, head temperature is 285 ± 10 ℃, 250～350 revs/min of screw speeds.
The technical problem to be solved in the present invention is, hard and crisp for high temperature resistant nylon resin in prior art, the shortcoming that mobility is poor, the intensity difference existing when liquid crystalline polymers is used separately and the shortcoming of poor rigidity, the present invention utilizes liquid crystalline polymers can improve toughness and the crystallization rate of semi-aromatic nylon, utilize semi-aromatic nylon can improve intensity and the rigidity of liquid crystalline polymers, the two is in conjunction with having brought into play the effect of learning from other's strong points to offset one's weaknesses, utilize the advantage of HNTs self structure simultaneously, with high temperature resistant nylon can well be compatible, and self is better dispersed, be difficult for reuniting, a kind of high strength is provided, high rigidity, the HPN/TLCP/HNTs matrix material of resistance toheat and chemical stability excellence.
Compared with prior art, beneficial effect of the present invention is as follows:
First, it is raw material that the present invention adopts semi-aromatic nylon and liquid crystalline polymers, and added a kind of special filling toughener-HNTs nanotube, make semi-aromatic nylon resin and liquid crystalline polymers compound under molten state, utilize the advantage of HNTs self structure, can there is good consistency with high temperature resistant nylon, and self is better dispersed, be difficult for reuniting, obtained the HPN/TLCP/HNTs matrix material of a kind of high strength, high rigidity, thermotolerance and chemical stability Good All-around Property excellence.
Second, semi-aromatic nylon of the present invention and Liquid Crystal Polymer alloys Material Addition the relatively cheap HNTs of price, the too high drawback of use cost of having avoided independent use high temperature resistant nylon and TLCP and having occurred, thereby reduced cost, and preparation method's technique is simple, can obtain good economic benefit.
Embodiment
Below in conjunction with specific embodiment, the present invention is further described.The diameter of halloysite nanotubes in the following example (HNTs) is 50～100 μ m.
Embodiment 1
A kind of HPN/TLCP/HNTs nanometer tube composite materials, raw material by following parts by weight is made: semi-aromatic nylon PA10T70 part, liquid crystalline polymers 5130L5 part, 10 parts of HNTs nanotubes, 0.5 part of maleic anhydride, 1 part of calcium stearate lubricant, 0.5 part, oxidation inhibitor, wherein oxidation inhibitor is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester; Its preparation method is:
(1) first by high temperature resistant nylon resin, liquid crystalline polymers and halloysite nanotubes respectively at 120 ℃, 140 ℃ and 90 ℃ of forced air dryings 10 hours;
(2) utilize homogenizer to carry out, after high-speed mixing, putting into loft drier and being dried to lubricant, oxidation inhibitor and compatilizer, drying temperature is 90 ℃, and be 3 hours time of drying;
(3) raw material of step (1) (2) being handled well is put in high-speed mixer, evenly mixes 5min;
(4) raw material mixing in step (3) is put in the loading hopper of twin screw extruder, through melt extruding, granulation; Each of twin screw extruder section Temperature Setting is: 275 ℃ of district's temperature, two 275 ℃ of district's temperature, three 280 ℃ of district's temperature, four 285 ℃ of district's temperature, five 295 ℃ of district's temperature, six 295 ℃ of district's temperature, seven 295 ℃ of district's temperature, eight 290 ℃ of district's temperature, nine 285 ℃ of district's temperature, ten 285 ℃ of district's temperature, head temperature is 285 ℃, 250 revs/min of screw speeds.
Embodiment 2
A kind of HPN/TLCP/HNTs nanometer tube composite materials, raw material by following parts by weight is made: semi-aromatic nylon PA10T75 part, liquid crystalline polymers 5130L10 part, 15 parts of HNTs nanotubes, 0.5 part of maleic anhydride, 1 part of calcium stearate lubricant, 0.5 part, oxidation inhibitor, wherein oxidation inhibitor is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester; Its preparation method is:
(1) first by high temperature resistant nylon resin, liquid crystalline polymers and halloysite nanotubes respectively at 130 ℃, 150 ℃ and 100 ℃ of forced air dryings 8 hours;
(2) utilize homogenizer to carry out, after high-speed mixing, putting into loft drier and being dried to lubricant, oxidation inhibitor and compatilizer, drying temperature is 100 ℃, and be 1 hour time of drying;
(3) raw material of step (1) (2) being handled well is put in high-speed mixer, evenly mixes 8min;
(4) raw material mixing in step (3) is put in the loading hopper of twin screw extruder, through melt extruding, granulation; Each of twin screw extruder section Temperature Setting is: 285 ℃ of district's temperature, two 285 ℃ of district's temperature, three 290 ℃ of district's temperature, four 295 ℃ of district's temperature, five 305 ℃ of district's temperature, six 305 ℃ of district's temperature, seven 305 ℃ of district's temperature, eight 300 ℃ of district's temperature, nine 295 ℃ of district's temperature, ten 295 ℃ of district's temperature, head temperature is 295 ℃, 300 revs/min of screw speeds.
Embodiment 3
A kind of HPN/TLCP/HNTs nanometer tube composite materials, raw material by following parts by weight is made: semi-aromatic nylon PA10T80 part, liquid crystalline polymers 5130L15 part, 20 parts of HNTs nanotubes, 0.5 part of maleic anhydride, 1 part of calcium stearate lubricant, 0.5 part, oxidation inhibitor, wherein oxidation inhibitor is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester; Its preparation method is:
(1) first by high temperature resistant nylon resin, liquid crystalline polymers and halloysite nanotubes respectively at 125 ℃, 145 ℃ and 95 ℃ of forced air dryings 9 hours;
(2) utilize homogenizer to carry out, after high-speed mixing, putting into loft drier and being dried to lubricant, oxidation inhibitor and compatilizer, drying temperature is 95 ℃, and be 2 hours time of drying;
(3) raw material of step (1) (2) being handled well is put in high-speed mixer, evenly mixes 10min;
(4) raw material mixing in step (3) is put in the loading hopper of twin screw extruder, through melt extruding, granulation; Each of twin screw extruder section Temperature Setting is: 265 ℃ of district's temperature, two 265 ℃ of district's temperature, three 270 ℃ of district's temperature, four 275 ℃ of district's temperature, five 285 ℃ of district's temperature, six 285 ℃ of district's temperature, seven 285 ℃ of district's temperature, eight 280 ℃ of district's temperature, nine 275 ℃ of district's temperature, ten 275 ℃ of district's temperature, head temperature is 275 ℃, 350 revs/min of screw speeds.
Embodiment 4
A kind of HPN/TLCP/HNTs nanometer tube composite materials, raw material by following parts by weight is made: the 5130L of semi-aromatic nylon PA9T70 part, liquid crystalline polymers 5130L(E.I.Du Pont Company) 15 parts, 20 parts of HNTs nanotubes, 0.3 part of maleic anhydride, 0.5 part of calcium stearate lubricant, 0.3 part, oxidation inhibitor, wherein oxidation inhibitor is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester; Its preparation method is:
(1) first by high temperature resistant nylon resin, liquid crystalline polymers and halloysite nanotubes respectively at 120 ℃, 145 ℃ and 100 ℃ of forced air dryings 8 hours;
(2) utilize homogenizer to carry out, after high-speed mixing, putting into loft drier and being dried to lubricant, oxidation inhibitor and compatilizer, drying temperature is 100 ℃, and be 1 hour time of drying;
(3) raw material of step (1) (2) being handled well is put in high-speed mixer, evenly mixes 6min;
(4) raw material mixing in step (3) is put in the loading hopper of twin screw extruder, through melt extruding, granulation; Each of twin screw extruder section Temperature Setting is: 270 ℃ of district's temperature, two 270 ℃ of district's temperature, three 280 ℃ of district's temperature, four 285 ℃ of district's temperature, five 290 ℃ of district's temperature, six 290 ℃ of district's temperature, seven 290 ℃ of district's temperature, eight 275 ℃ of district's temperature, nine 280 ℃ of district's temperature, ten 280 ℃ of district's temperature, head temperature is 280 ℃, 250 revs/min of screw speeds.
Embodiment 5
A kind of HPN/TLCP/HNTs nanometer tube composite materials, raw material by following parts by weight is made: semi-aromatic nylon PA12T80 part, liquid crystalline polymers 5130L10 part, 15 parts of HNTs nanotubes, 0.2 part of maleic anhydride, 0.3 part of calcium stearate lubricant, 0.2 part, oxidation inhibitor, wherein oxidation inhibitor is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester; Its preparation method is:
(1) first by high temperature resistant nylon resin, liquid crystalline polymers and halloysite nanotubes respectively at 130 ℃, 140 ℃ and 100 ℃ of forced air dryings 8 hours;
(2) utilize homogenizer to carry out, after high-speed mixing, putting into loft drier and being dried to lubricant, oxidation inhibitor and compatilizer, drying temperature is 100 ℃, and be 1 hour time of drying;
(3) raw material of step (1) (2) being handled well is put in high-speed mixer, evenly mixes 10min;
(4) raw material mixing in step (3) is put in the loading hopper of twin screw extruder, through melt extruding, granulation; Each of twin screw extruder section Temperature Setting is: 280 ℃ of district's temperature, two 280 ℃ of district's temperature, three 285 ℃ of district's temperature, four 290 ℃ of district's temperature, five 300 ℃ of district's temperature, six 300 ℃ of district's temperature, seven 300 ℃ of district's temperature, eight 295 ℃ of district's temperature, nine 290 ℃ of district's temperature, ten 290 ℃ of district's temperature, head temperature is 290 ℃, 280 revs/min of screw speeds.
Embodiment 6
A kind of HPN/TLCP/HNTs nanometer tube composite materials, raw material by following parts by weight is made: semi-aromatic nylon PA10T70 part, liquid crystalline polymers 5130L10 part, 20 parts of HNTs nanotubes, 0.2 part of maleic anhydride, 0.3 part of lubricant, the mixture of internal lubricant calcium stearate and external lubricant polysiloxane wherein, both ratios are 0.2 part, 1:1, oxidation inhibitor, wherein oxidation inhibitor is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester; Its preparation method is:
(1) first by high temperature resistant nylon resin, liquid crystalline polymers and halloysite nanotubes respectively at 130 ℃, 145 ℃ and 95 ℃ of forced air dryings 8 hours;
(2) utilize homogenizer to carry out, after high-speed mixing, putting into loft drier and being dried to lubricant, oxidation inhibitor and compatilizer, drying temperature is 100 ℃, and be 1 hour time of drying;
(3) raw material of step (1) (2) being handled well is put in high-speed mixer, evenly mixes 9min;
(4) raw material mixing in step (3) is put in the loading hopper of twin screw extruder, through melt extruding, granulation; Each of twin screw extruder section Temperature Setting is: 280 ℃ of district's temperature, two 280 ℃ of district's temperature, three 285 ℃ of district's temperature, four 295 ℃ of district's temperature, five 300 ℃ of district's temperature, six 305 ℃ of district's temperature, seven 295 ℃ of district's temperature, eight 295 ℃ of district's temperature, nine 290 ℃ of district's temperature, ten 290 ℃ of district's temperature, head temperature is 290 ℃, 300 revs/min of screw speeds.
Embodiment 7
A kind of HPN/TLCP/HNTs nanometer tube composite materials, raw material by following parts by weight is made: semi-aromatic nylon PA8T75 part, liquid crystalline polymers 5130L10 part, 15 parts of HNTs nanotubes, 0.2 part of maleic anhydride, 0.3 part of lubricant, the mixture of internal lubricant calcium stearate and external lubricant silicon-dioxide wherein, both ratios are 0.2 part, 1:1, oxidation inhibitor, wherein oxidation inhibitor is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester; Its preparation method is:
(1) first by high temperature resistant nylon resin, liquid crystalline polymers and halloysite nanotubes respectively at 130 ℃, 135 ℃ and 95 ℃ of forced air dryings 8.5 hours;
(2) utilize homogenizer to carry out, after high-speed mixing, putting into loft drier and being dried to lubricant, oxidation inhibitor and compatilizer, drying temperature is 95 ℃, and be 2 hours time of drying;
(3) raw material of step (1) (2) being handled well is put in high-speed mixer, evenly mixes 10min;
(4) raw material mixing in step (3) is put in the loading hopper of twin screw extruder, through melt extruding, granulation; Each of twin screw extruder section Temperature Setting is: 265 ℃ of district's temperature, two 275 ℃ of district's temperature, three 275 ℃ of district's temperature, four 280 ℃ of district's temperature, five 290 ℃ of district's temperature, six 285 ℃ of district's temperature, seven 290 ℃ of district's temperature, eight 285 ℃ of district's temperature, nine 280 ℃ of district's temperature, ten 280 ℃ of district's temperature, head temperature is 280 ℃, 320 revs/min of screw speeds.
Embodiment 8
A kind of HPN/TLCP/HNTs nanometer tube composite materials, raw material by following parts by weight is made: semi-aromatic nylon PA9T70 part, liquid crystalline polymers 5130L10 part, 20 parts of HNTs nanotubes, 0.2 part of maleic anhydride, 0.3 part of lubricant, the mixture of internal lubricant paraffin and external lubricant polysiloxane wherein, both ratios are 0.2 part, 1:1, oxidation inhibitor, wherein oxidation inhibitor is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester; Its preparation method is:
(1) first by high temperature resistant nylon resin, liquid crystalline polymers and halloysite nanotubes respectively at 125 ℃, 145 ℃ and 100 ℃ of forced air dryings 9.5 hours;
(2) utilize homogenizer to carry out, after high-speed mixing, putting into loft drier and being dried to lubricant, oxidation inhibitor and compatilizer, drying temperature is 95 ℃, and be 2 hours time of drying;
(3) raw material of step (1) (2) being handled well is put in high-speed mixer, evenly mixes 10min;
(4) raw material mixing in step (3) is put in the loading hopper of twin screw extruder, through melt extruding, granulation; Each of twin screw extruder section Temperature Setting is: 270 ℃ of district's temperature, two 270 ℃ of district's temperature, three 285 ℃ of district's temperature, four 295 ℃ of district's temperature, five 300 ℃ of district's temperature, six 300 ℃ of district's temperature, seven 305 ℃ of district's temperature, eight 300 ℃ of district's temperature, nine 305 ℃ of district's temperature, ten 300 ℃ of district's temperature, head temperature is 300 ℃, 300 revs/min of screw speeds.
Embodiment 9
A kind of HPN/TLCP/HNTs nanometer tube composite materials, raw material by following parts by weight is made: semi-aromatic nylon PA12T80 part, liquid crystalline polymers 5130L10 part, 15 parts of HNTs nanotubes, 0.2 part of maleic anhydride, 0.3 part of lubricant, the mixture of internal lubricant paraffin and external lubricant silicon-dioxide wherein, both ratios are 0.2 part, 1:1, oxidation inhibitor, wherein oxidation inhibitor is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester; Its preparation method is:
(1) first by high temperature resistant nylon resin, liquid crystalline polymers and halloysite nanotubes respectively at 120 ℃, 140 ℃ and 90 ℃ of forced air dryings 10 hours;
(2) utilize homogenizer to carry out, after high-speed mixing, putting into loft drier and being dried to lubricant, oxidation inhibitor and compatilizer, drying temperature is 90 ℃, and be 3 hours time of drying;
(3) raw material of step (1) (2) being handled well is put in high-speed mixer, evenly mixes 5min;
(4) raw material mixing in step (3) is put in the loading hopper of twin screw extruder, through melt extruding, granulation; Each of twin screw extruder section Temperature Setting is: 280 ℃ of district's temperature, two 285 ℃ of district's temperature, three 285 ℃ of district's temperature, four 295 ℃ of district's temperature, five 285 ℃ of district's temperature, six 290 ℃ of district's temperature, seven 295 ℃ of district's temperature, eight 295 ℃ of district's temperature, nine 290 ℃ of district's temperature, ten 290 ℃ of district's temperature, head temperature is 295 ℃, 350 revs/min of screw speeds.Prepared a kind of HPN/TLCP/HNTs nanometer tube composite materials in above-described embodiment, all there is excellent mechanical property, can be used as the materials'use of making various heat-resistant antifriction component in automobile, electric industry, simultaneously because TLCP has extraordinary flame retardant properties, the flame retardant properties of the product that this invention is produced is far away higher than the general flame retardant properties of material.The concrete test data of its performance is listed in the table below 1:
Table 1
| Performance | Testing method | Unit | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Tensile strength | ASTM?D638 | MPa | 102 | 113 | 127 |
| Flexural strength | ASTM?D790 | MPa | 198 | 235 | 252 |
| Modulus in flexure | ASTM?D790 | MPa | 11756 | 12876 | 14697 |
| Izod notched Izod impact strength | ASTM?D256 | KJ/m 2 | 19 | 24 | 29 |
| Heat-drawn wire | ISO75-2 | ℃ | 255 | 263 | 274 |
The above-mentioned description to embodiment is can understand and apply the invention for ease of those skilled in the art.Person skilled in the art obviously can easily make various modifications to these embodiment, and General Principle described herein is applied in other embodiment and needn't passes through performing creative labour.Therefore, the invention is not restricted to the embodiment here, those skilled in the art are according to announcement of the present invention, and not departing from the improvement that category of the present invention makes and revise all should be within protection scope of the present invention.
Claims (10)
1. semi-aromatic nylon/TLCP/halloysite nanotubes matrix material, is characterized in that: by the component that comprises following weight part, made:
Semi-aromatic nylon 70-80 part,
TLCP 5-15 part,
Halloysite nanotubes 10-20 part,
Compatilizer 0.2-0.5 part,
Lubricant 0.3-1.0 part,
Oxidation inhibitor 0.2-0.5 part.
2. semi-aromatic nylon/TLCP according to claim 1/halloysite nanotubes matrix material, it is characterized in that: described semi-aromatic nylon is selected from one or more in PA6T, PA7T, PA8T, PA9T, PA10T or PA12T, be preferably one or more in PA9T, PA10T or PA12T.
3. semi-aromatic nylon/TLCP according to claim 1/halloysite nanotubes matrix material, it is characterized in that: described liquid crystalline polymers comprises all aromatic TLCP or semi-aromatic TLCP, preferably the 5130L of Du Pont or Polyplastics E130i.
4. semi-aromatic nylon/TLCP according to claim 1/halloysite nanotubes matrix material, is characterized in that: the diameter of described halloysite nanotubes is 50～100 μ m.
5. semi-aromatic nylon/TLCP according to claim 1/halloysite nanotubes matrix material, is characterized in that: described compatilizer is selected from one or more in toxilic acid, maleic anhydride, fumaric acid, methylene-succinic acid or glycidyl acrylate; Be preferably one or more in maleic anhydride or toxilic acid.
6. semi-aromatic nylon/TLCP according to claim 1/halloysite nanotubes matrix material, is characterized in that: described lubricant comprises one or more in internal lubricant or external lubricant.
7. semi-aromatic nylon/TLCP according to claim 6/halloysite nanotubes matrix material, it is characterized in that: described internal lubricant is fatty acid amide series lubricant agent or hydro carbons lubricant, wherein fatty acid amide series lubricant agent is N, N '-bis-ethylene hard fatty acids acid amides, stearic amide or amine hydroxybenzene; Described hydro carbons lubricant is paraffin, polyethylene wax or Poly Propylene Wax;
Or described external lubricant is nonpolar lubricant, described nonpolar lubricant is siloxanes, silicon-dioxide or diatomite.
8. semi-aromatic nylon/TLCP according to claim 1/halloysite nanotubes matrix material, it is characterized in that: described oxidation inhibitor is phenols high-temperature antioxidant, be selected from four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, β-(3,5-di-tert-butyl-hydroxy phenyl) the positive octadecanol ester of propionic acid or 1,3,5-tri-(the 4-tertiary butyl-3-hydroxyl-2,6-dimethyl benzyl)-1,3,5-triazines-2,4, one or more in 6-(1H, 3H, 5H)-triketone.
9. a preparation method for arbitrary described semi-aromatic nylon/TLCP/halloysite nanotubes matrix material in claim 1-8, is characterized in that: comprise the following steps:
(1) first that high temperature resistant nylon resin, liquid crystalline polymers, halloysite nanotubes is dry respectively;
(2) lubricant, processing aid and compatilizer are mixed, dry;
(3) raw material of step (1), (2) being handled well mixes;
(4) raw material mixing in step (3) is melt extruded to granulation through twin screw extruder.
10. preparation method according to claim 9, it is characterized in that: in described step (1), semi-aromatic nylon resin, liquid crystalline polymers and halloysite nanotubes were respectively at 120～130 ℃, 140～150 ℃ and 90～100 ℃ of forced air dryings 8～10 hours;
Or in described step (2), utilize homogenizer to carry out, after high-speed mixing, putting into loft drier and being dried to lubricant, oxidation inhibitor and compatilizer, and drying temperature is 90～100 ℃, be 1～3 hour time of drying;
Or in described step (3), mixing time is 5～10min;
Or in described step (4), each of twin screw extruder section Temperature Setting is: 275 ± 10 ℃ of district's temperature, two 275 ± 10 ℃ of district's temperature, three 280 ± 10 ℃ of district's temperature, four 285 ± 10 ℃ of district's temperature, five 295 ± 10 ℃ of district's temperature, six 295 ± 10 ℃ of district's temperature, seven 295 ± 10 ℃ of district's temperature, eight 290 ± 10 ℃ of district's temperature, nine 285 ± 10 ℃ of district's temperature, ten 285 ± 10 ℃ of district's temperature, head temperature is 285 ± 10 ℃, 250～350 revs/min of screw speeds.
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