CN104098890B - A kind of HPN/TLCP/HNTs composite material and preparation methods - Google Patents

A kind of HPN/TLCP/HNTs composite material and preparation methods Download PDF

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CN104098890B
CN104098890B CN201310122617.6A CN201310122617A CN104098890B CN 104098890 B CN104098890 B CN 104098890B CN 201310122617 A CN201310122617 A CN 201310122617A CN 104098890 B CN104098890 B CN 104098890B
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liquid crystal
crystal polymer
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CN104098890A (en
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杨桂生
李宗仁
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Shanghai Genius Advanced Materials Group Co Ltd
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    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
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    • B29C48/04—Particle-shaped
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
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    • B29C48/25—Component parts, details or accessories; Auxiliary operations
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    • B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
    • B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C2948/00—Indexing scheme relating to extrusion moulding
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Abstract

The invention belongs to engineering plastics technical field, it is related to a kind of HPN/TLCP/HNTs nanometer tube composite materials and preparation method thereof.The material is made of the component comprising following parts 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 parts of compatilizer, 0.3 1.0 parts of lubricant, 0.2 0.5 parts of antioxidant.Compared with prior art, HNTs in the present invention can have good compatibility with high temperature resistant nylon, and itself dispersibility is preferably, is not easy to reunite, to obtain a kind of high intensity, high rigidity, heat resistance and the excellent HPN/TLCP/HNTs composite materials of chemical stability；It is added to the relatively cheap HNTs of price in the composite material of the present invention, avoids and high temperature resistant nylon and TLCP is used alone and the excessively high drawback of the use cost that occurs, and preparation method is simple for process.

Description

A kind of HPN/TLCP/HNTs composite material and preparation methods
Technical field
The invention belongs to engineering plastics technical fields, are related to a kind of semi-aromatic nylon/thermotropic liquid crystal polymer/Ai Luo Stone nanotube（HPN/TLCP/HNTs）Composite material and preparation method.
Background technology
Recent decades, nylon have significant progress in industry in life.But recent years is due to electric work The development of industry, especially SMT（Surface mounted technology）Be widely used so that in the industry to properties such as material high temperature resistants Requirement it is higher and higher.And high temperature resistant nylon relies on its high-melting-point, good mechanical performance gradually to be opened in the industry existing The a piece of world.
Presently used most high temperature resistant nylon is DSM（Royal DSM）PA46, but due to PA46 be amorphous nylon, In high temperature resistant and mechanical properties still not as good as aromatic series or semi-aromatic nylon.Therefore, as PA6T, PA9T, PA10T semiaromatic Race's nylon has been greatly developed.But the poor fluidity of high temperature resistant nylon, processing performance are bad, mechanical performance cannot meet The shortcomings of industrial requirements, is increasingly apparent, therefore seeks the excellent high temperature resistant Buddhist nun of a kind of mechanical property, processing performance, mobile performance Dragon is particularly important.Thermotropic liquid crystal polymer（TLCP）With excellent mechanical property, obtained in many high-technology fields To being widely applied.Liquid crystal polymerNot onlyWith high intensity, the mechanical property of high-modulus, also there is excellent thermal stability With mobility, heat resistance and chemical resistance, and it is wear-resisting, anti-attrition is excellent.Against weather, the radiation resistance of TLCP is good It is good, there is excellent anti-flammability, can knock down the flame and do not continue to burn.Its combustion rating reaches UL94V-0 grades of levels.
Galapectite（HNTs）It is a kind of natural many walls nanotube shape material, by oxygen-octahedron and alumina octahedral group At belonging to kaolinite class.Since HNTs outer walls contain certain hydroxyl, there is polarity, hydrogen bond can be formed with high temperature resistant nylon, and And the Interaction Force of HNTs is not strong, is easily dispersed.Therefore, the addition of HNTs can improve HPN/TLCP/HNTs composite woods The comprehensive performance of material, reduces cost.
The present invention provides a kind of high intensity, high rigidity, heat resistance and the excellent HPN/TLCP/HNTs of chemical stability Composite material, in the composite, semi-aromatic nylon and liquid crystal polymer make up for each other's deficiencies and learn from each other, and have both improved semi-aromatic Buddhist nun The toughness and crystalline rate of dragon, and the intensity and rigidity of liquid crystal polymer are improved, the addition of HNTs nano-tube materials can increase The mechanical performance of strong composite material；Thus prepared composite material has excellent comprehensive performance.And it is produced by the present invention HPN/TLCP/HNTs composite materials keep semi-aromatic nylon, liquid crystal polymer material original while with superhigh intensity Other every excellent physical and mechanical properties.
Invention content
It is an object of the invention to provide a kind of semi-aromatic nylon/thermotropic liquid crystal to overcome the deficiencies of existing technologies Polymer/halloysite nanotubes（HPN/TLCP/HNTs）Composite material and preparation method.
To achieve the above object, the present invention uses following technical scheme：
A kind of semi-aromatic nylon/thermotropic liquid crystal polymer/halloysite nanotubes（HPN/TLCP/HNTs）Composite wood Material, is made of the component comprising following parts by weight：
70-80 parts of semi-aromatic nylon (HPN),
5-15 parts of thermotropic liquid crystal polymer (TLCP),
10-20 parts of halloysite nanotubes (HNTs),
0.2-0.5 parts of compatilizer,
0.3-1.0 parts of lubricant,
0.2-0.5 parts of antioxidant.
The one kind or one kind of the semi-aromatic nylon in PA6T, PA7T, PA8T, PA9T, PA10T or PA12T More than, the one or more preferably in PA9T, PA10T or PA12T.
The liquid crystal polymer includes all aromatic thermotropic liquid crystal polymer or semi-aromatic thermotropic liquid crystal polymer.Heat Cause property liquid crystal polymer is mainly by P-hydroxybenzoic acid（HBA）, hydroquinone（HQ）, mixing aromatic diacid（MA）, isophthalic two Formic acid（IA）, terephthalic acid (TPA) (TA), 4.4 '-dicarboxyl-N- phenylbenzamaides（NA）, 4.4 '-oxydibenzoic acids, connection The polymer of the repetitive unit composition of the extractions such as benzene, polymer containing naphthalene nucleus, preferably Du Pont 5130L or Polyplastics E130i etc..
The halloysite nanotubes（HNTs）A diameter of 50~100 μm.
The compatilizer is that can interact with liquid crystal polymer and semi-aromatic nylon resin or both Polyfunctional compound, be physical compatilizer or chemically solubilizer；It is further selected from maleic acid, maleic anhydride, rich horse One or more in acid, itaconic acid or glycidyl acrylate；One kind preferably in maleic anhydride or maleic acid Or more than one.
The lubricant includes the one or more in in-lubricant or external lubricant.
The in-lubricant is fatty acid amide series lubricant agent or hydrocarbon lubricants, wherein fatty acid amide series lubricant agent For N, the bis- ethylene hard fatty acids amides of N '-, stearic amide or oleamide；The hydrocarbon lubricants are paraffin, polyethylene Wax or polypropylene wax.
The external lubricant is non-polar lubricant, and the non-polar lubricant is siloxanes, silica or silicon Diatomaceous earth etc..
The antioxidant is phenols high-temperature antioxidant, is selected from four [β-（3,5- di-tert-butyl-hydroxy phenyls）Propionic acid] Pentaerythritol ester, β-（3,5- di-tert-butyl-hydroxy phenyls）Propionic acid n-octadecyl alcohol ester or the (4- tertiary butyls -3- of 1,3,5- tri- Hydroxyl -2,6- dimethyl benzyls) one or more in -1,3,5- triazines -2,4,6- (1H, 3H, 5H)-triketone.
A kind of preparation method of above-mentioned HPN/TLCP/HNTs composite materials, includes the following steps：
（1）First high temperature resistant nylon resin, liquid crystal polymer, halloysite nanotubes are separately dried；
（2）Lubricant, processing aid and compatilizer are uniformly mixed, it is dry；
（3）By step（1）、（2）The raw material handled well is uniformly mixed；
（4）By step（3）In the raw material that mixes through double screw extruder melting extrusion, be granulated.
The step（1）In, semi-aromatic nylon resin, liquid crystal polymer and halloysite nanotubes respectively at 120~ 130 DEG C, 140~150 DEG C and 90~100 DEG C forced air dryings 8~10 hours；
The step（2）In, after carrying out mixed at high speed to lubricant, antioxidant and compatilizer using homogenizer, It is put into drying box and is dried, drying temperature is 90~100 DEG C, and drying time is 1~3 hour；
The step（3）In, incorporation time is 5~10min.
The step（4）In, the temperature of each section of double screw extruder is set as：One 275 ± 10 DEG C of area's temperature, two area's temperature 275 ± 10 DEG C of degree, three 280 ± 10 DEG C of area's temperature, four 285 ± 10 DEG C of area's temperature, five 295 ± 10 DEG C of area's temperature, six area's temperature 295 ± 10 DEG C, seven 295 ± 10 DEG C of area's temperature, eight 290 ± 10 DEG C of area's temperature, nine 285 ± 10 DEG C of area's temperature, ten area's temperature 285 ± 10 DEG C, head temperature is 285 ± 10 DEG C, 250~350 revs/min of screw speed.
The technical problem to be solved in the present invention is, the hard and crisp, mobility for high temperature resistant nylon resin in the prior art Poor disadvantage, existing intensity difference and the shortcomings that poor rigidity when liquid crystal polymer is used alone, the present invention utilizes polymerizable mesogenic Object can improve the toughness and crystalline rate of semi-aromatic nylon, using semi-aromatic nylon can be improved liquid crystal polymer intensity and Rigidity, the two combine and have played the effect learnt from other's strong points to offset one's weaknesses, while the advantages of using HNTs self structures, can be with high temperature resistant nylon It is compatible well, and itself dispersibility is preferably, is not easy to reunite, and it is steady to provide a kind of high intensity, high rigidity, heat resistance and chemistry Surely the HPN/TLCP/HNTs composite materials haveing excellent performance.
Compared with prior art, beneficial effects of the present invention are as follows：
First, the present invention uses semi-aromatic nylon and liquid crystal polymer for raw material, and is added to a kind of special filling Reinforcing agent-HNTs nanotubes, keep semi-aromatic nylon resin and liquid crystal polymer compound in the molten state, utilize HNTs itself The advantages of structure, can there is good compatibility with high temperature resistant nylon, and itself dispersibility is preferably, is not easy to reunite, obtain A kind of high intensity, high rigidity, heat resistance and the excellent HPN/TLCP/HNTs composite woods of chemical stability Good All-around Property Material.
Second, it is relatively cheap that semi-aromatic nylon of the invention and Liquid Crystal Polymer alloys material are added to price HNTs is avoided and high temperature resistant nylon and TLCP is used alone and the excessively high drawback of the use cost that occurs, to reduce cost, And preparation method is simple for process, can obtain good economic benefit.
Specific implementation mode
With reference to specific embodiment, invention is further explained.Halloysite nanotubes in the following example （HNTs）A diameter of 50~100 μm.
Embodiment 1
A kind of HPN/TLCP/HNTs nanometer tube composite materials, are prepared from the following raw materials in parts by weight：Semi-aromatic nylon PA10T70 parts, 5130L5 parts of liquid crystal polymer, 10 parts of HNTs nanotubes, 0.5 part of maleic anhydride, 1 part of calcium stearate lubricant, 0.5 part of antioxidant, wherein antioxidant are four [β-（3,5- di-tert-butyl-hydroxy phenyls）Propionic acid] pentaerythritol ester；It is prepared Method is：
（1）First by high temperature resistant nylon resin, liquid crystal polymer and halloysite nanotubes respectively at 120 DEG C, 140 DEG C and 90 DEG C Forced air drying 10 hours；
（2）Using homogenizer to lubricant, antioxidant and compatilizer carry out mixed at high speed after, be put into drying box into Row drying, drying temperature are 90 DEG C, and drying time is 3 hours；
（3）By step（1）（2）The raw material handled well is put into high-speed mixer, and 5min is uniformly mixed；
（4）By step（3）In the raw material that mixes put into the loading hopper of double screw extruder, through melting extrusion, make Grain；The temperature of each section of double screw extruder is set as：One 275 DEG C of area's temperature, two 275 DEG C of area's temperature, three 280 DEG C of area's temperature, four 285 DEG C of area's temperature, five 295 DEG C of area's temperature, six 295 DEG C of area's temperature, seven 295 DEG C of area's temperature, eight 290 DEG C of area's temperature, nine area's temperature 285 DEG C, ten 285 DEG C of area's temperature, head temperature is 285 DEG C, 250 revs/min of screw speed.
Embodiment 2
A kind of HPN/TLCP/HNTs nanometer tube composite materials, are prepared from the following raw materials in parts by weight：Semi-aromatic nylon PA10T75 parts, 5130L10 parts of liquid crystal polymer, 15 parts of HNTs nanotubes, 0.5 part of maleic anhydride, 1 part of calcium stearate lubricant, 0.5 part of antioxidant, wherein antioxidant are four [β-（3,5- di-tert-butyl-hydroxy phenyls）Propionic acid] pentaerythritol ester；It is prepared Method is：
（1）First by high temperature resistant nylon resin, liquid crystal polymer and halloysite nanotubes respectively at 130 DEG C, 150 DEG C and 100 DEG C forced air drying 8 hours；
（2）Using homogenizer to lubricant, antioxidant and compatilizer carry out mixed at high speed after, be put into drying box into Row drying, drying temperature are 100 DEG C, and drying time is 1 hour；
（3）By step（1）（2）The raw material handled well is put into high-speed mixer, and 8min is uniformly mixed；
（4）By step（3）In the raw material that mixes put into the loading hopper of double screw extruder, through melting extrusion, make Grain；The temperature of each section of double screw extruder is set as：One 285 DEG C of area's temperature, two 285 DEG C of area's temperature, three 290 DEG C of area's temperature, four 295 DEG C of area's temperature, five 305 DEG C of area's temperature, six 305 DEG C of area's temperature, seven 305 DEG C of area's temperature, eight 300 DEG C of area's temperature, nine area's temperature 295 DEG C, ten 295 DEG C of area's temperature, head temperature is 295 DEG C, 300 revs/min of screw speed.
Embodiment 3
A kind of HPN/TLCP/HNTs nanometer tube composite materials, are prepared from the following raw materials in parts by weight：Semi-aromatic nylon PA10T80 parts, 5130L15 parts of liquid crystal polymer, 20 parts of HNTs nanotubes, 0.5 part of maleic anhydride, 1 part of calcium stearate lubricant, 0.5 part of antioxidant, wherein antioxidant are four [β-（3,5- di-tert-butyl-hydroxy phenyls）Propionic acid] pentaerythritol ester；It is prepared Method is：
（1）First by high temperature resistant nylon resin, liquid crystal polymer and halloysite nanotubes respectively at 125 DEG C, 145 DEG C and 95 DEG C Forced air drying 9 hours；
（2）Using homogenizer to lubricant, antioxidant and compatilizer carry out mixed at high speed after, be put into drying box into Row drying, drying temperature are 95 DEG C, and drying time is 2 hours；
（3）By step（1）（2）The raw material handled well is put into high-speed mixer, and 10min is uniformly mixed；
（4）By step（3）In the raw material that mixes put into the loading hopper of double screw extruder, through melting extrusion, make Grain；The temperature of each section of double screw extruder is set as：One 265 DEG C of area's temperature, two 265 DEG C of area's temperature, three 270 DEG C of area's temperature, four 275 DEG C of area's temperature, five 285 DEG C of area's temperature, six 285 DEG C of area's temperature, seven 285 DEG C of area's temperature, eight 280 DEG C of area's temperature, nine area's temperature 275 DEG C, ten 275 DEG C of area's temperature, head temperature is 275 DEG C, 350 revs/min of screw speed.
Embodiment 4
A kind of HPN/TLCP/HNTs nanometer tube composite materials, are prepared from the following raw materials in parts by weight：Semi-aromatic nylon PA9T70 parts, liquid crystal polymer 5130L（The 5130L of E.I.Du Pont Company）15 parts, it is 20 parts of HNTs nanotubes, 0.3 part of maleic anhydride, hard 0.5 part of resin acid calcium lubricant, 0.3 part of antioxidant, wherein antioxidant are four [β-（3,5- di-tert-butyl-hydroxy phenyls）Propionic acid] Pentaerythritol ester；Preparation method is：
（1）First by high temperature resistant nylon resin, liquid crystal polymer and halloysite nanotubes respectively at 120 DEG C, 145 DEG C and 100 DEG C forced air drying 8 hours；
（2）Using homogenizer to lubricant, antioxidant and compatilizer carry out mixed at high speed after, be put into drying box into Row drying, drying temperature are 100 DEG C, and drying time is 1 hour；
（3）By step（1）（2）The raw material handled well is put into high-speed mixer, and 6min is uniformly mixed；
（4）By step（3）In the raw material that mixes put into the loading hopper of double screw extruder, through melting extrusion, make Grain；The temperature of each section of double screw extruder is set as：One 270 DEG C of area's temperature, two 270 DEG C of area's temperature, three 280 DEG C of area's temperature, four 285 DEG C of area's temperature, five 290 DEG C of area's temperature, six 290 DEG C of area's temperature, seven 290 DEG C of area's temperature, eight 275 DEG C of area's temperature, nine area's temperature 280 DEG C, ten 280 DEG C of area's temperature, head temperature is 280 DEG C, 250 revs/min of screw speed.
Embodiment 5
A kind of HPN/TLCP/HNTs nanometer tube composite materials, are prepared from the following raw materials in parts by weight：Semi-aromatic nylon PA12T80 parts, 5130L10 parts of liquid crystal polymer, 15 parts of HNTs nanotubes, 0.2 part of maleic anhydride, calcium stearate lubricant 0.3 Part, 0.2 part of antioxidant, wherein antioxidant are four [β-（3,5- di-tert-butyl-hydroxy phenyls）Propionic acid] pentaerythritol ester；It is made Preparation Method is：
（1）First by high temperature resistant nylon resin, liquid crystal polymer and halloysite nanotubes respectively at 130 DEG C, 140 DEG C and 100 DEG C forced air drying 8 hours；
（2）Using homogenizer to lubricant, antioxidant and compatilizer carry out mixed at high speed after, be put into drying box into Row drying, drying temperature are 100 DEG C, and drying time is 1 hour；
（3）By step（1）（2）The raw material handled well is put into high-speed mixer, and 10min is uniformly mixed；
（4）By step（3）In the raw material that mixes put into the loading hopper of double screw extruder, through melting extrusion, make Grain；The temperature of each section of double screw extruder is set as：One 280 DEG C of area's temperature, two 280 DEG C of area's temperature, three 285 DEG C of area's temperature, four 290 DEG C of area's temperature, five 300 DEG C of area's temperature, six 300 DEG C of area's temperature, seven 300 DEG C of area's temperature, eight 295 DEG C of area's temperature, nine area's temperature 290 DEG C, ten 290 DEG C of area's temperature, head temperature is 290 DEG C, 280 revs/min of screw speed.
Embodiment 6
A kind of HPN/TLCP/HNTs nanometer tube composite materials, are prepared from the following raw materials in parts by weight：Semi-aromatic nylon PA10T70 parts, 5130L10 parts of liquid crystal polymer, 20 parts of HNTs nanotubes, 0.2 part of maleic anhydride, 0.3 part of lubricant, wherein in The mixture of lubricant stearic acid calcium and external lubricant polysiloxanes, the two ratio are 1:1,0.2 part of antioxidant, wherein antioxidant For four [β-（3,5- di-tert-butyl-hydroxy phenyls）Propionic acid] pentaerythritol ester；Preparation method is：
（1）First by high temperature resistant nylon resin, liquid crystal polymer and halloysite nanotubes respectively at 130 DEG C, 145 DEG C and 95 DEG C Forced air drying 8 hours；
（2）Using homogenizer to lubricant, antioxidant and compatilizer carry out mixed at high speed after, be put into drying box into Row drying, drying temperature are 100 DEG C, and drying time is 1 hour；
（3）By step（1）（2）The raw material handled well is put into high-speed mixer, and 9min is uniformly mixed；
（4）By step（3）In the raw material that mixes put into the loading hopper of double screw extruder, through melting extrusion, make Grain；The temperature of each section of double screw extruder is set as：One 280 DEG C of area's temperature, two 280 DEG C of area's temperature, three 285 DEG C of area's temperature, four 295 DEG C of area's temperature, five 300 DEG C of area's temperature, six 305 DEG C of area's temperature, seven 295 DEG C of area's temperature, eight 295 DEG C of area's temperature, nine area's temperature 290 DEG C, ten 290 DEG C of area's temperature, head temperature is 290 DEG C, 300 revs/min of screw speed.
Embodiment 7
A kind of HPN/TLCP/HNTs nanometer tube composite materials, are prepared from the following raw materials in parts by weight：Semi-aromatic nylon PA8T75 parts, 5130L10 parts of liquid crystal polymer, 15 parts of HNTs nanotubes, 0.2 part of maleic anhydride, 0.3 part of lubricant, wherein in The mixture of lubricant stearic acid calcium and external lubricant silica, the two ratio are 1:1,0.2 part of antioxidant, wherein antioxidant For four [β-（3,5- di-tert-butyl-hydroxy phenyls）Propionic acid] pentaerythritol ester；Preparation method is：
（1）First by high temperature resistant nylon resin, liquid crystal polymer and halloysite nanotubes respectively at 130 DEG C, 135 DEG C and 95 DEG C Forced air drying 8.5 hours；
（2）Using homogenizer to lubricant, antioxidant and compatilizer carry out mixed at high speed after, be put into drying box into Row drying, drying temperature are 95 DEG C, and drying time is 2 hours；
（3）By step（1）（2）The raw material handled well is put into high-speed mixer, and 10min is uniformly mixed；
（4）By step（3）In the raw material that mixes put into the loading hopper of double screw extruder, through melting extrusion, make Grain；The temperature of each section of double screw extruder is set as：One 265 DEG C of area's temperature, two 275 DEG C of area's temperature, three 275 DEG C of area's temperature, four 280 DEG C of area's temperature, five 290 DEG C of area's temperature, six 285 DEG C of area's temperature, seven 290 DEG C of area's temperature, eight 285 DEG C of area's temperature, nine area's temperature 280 DEG C, ten 280 DEG C of area's temperature, head temperature is 280 DEG C, 320 revs/min of screw speed.
Embodiment 8
A kind of HPN/TLCP/HNTs nanometer tube composite materials, are prepared from the following raw materials in parts by weight：Semi-aromatic nylon PA9T70 parts, 5130L10 parts of liquid crystal polymer, 20 parts of HNTs nanotubes, 0.2 part of maleic anhydride, 0.3 part of lubricant, wherein in The mixture of lubricant paraffin and external lubricant polysiloxanes, the two ratio are 1:1,0.2 part of antioxidant, wherein antioxidant are four [β-（3,5- di-tert-butyl-hydroxy phenyls）Propionic acid] pentaerythritol ester；Preparation method is：
（1）First by high temperature resistant nylon resin, liquid crystal polymer and halloysite nanotubes respectively at 125 DEG C, 145 DEG C and 100 DEG C forced air drying 9.5 hours；
（2）Using homogenizer to lubricant, antioxidant and compatilizer carry out mixed at high speed after, be put into drying box into Row drying, drying temperature are 95 DEG C, and drying time is 2 hours；
（3）By step（1）（2）The raw material handled well is put into high-speed mixer, and 10min is uniformly mixed；
（4）By step（3）In the raw material that mixes put into the loading hopper of double screw extruder, through melting extrusion, make Grain；The temperature of each section of double screw extruder is set as：One 270 DEG C of area's temperature, two 270 DEG C of area's temperature, three 285 DEG C of area's temperature, four 295 DEG C of area's temperature, five 300 DEG C of area's temperature, six 300 DEG C of area's temperature, seven 305 DEG C of area's temperature, eight 300 DEG C of area's temperature, nine area's temperature 305 DEG C, ten 300 DEG C of area's temperature, head temperature is 300 DEG C, 300 revs/min of screw speed.
Embodiment 9
A kind of HPN/TLCP/HNTs nanometer tube composite materials, are prepared from the following raw materials in parts by weight：Semi-aromatic nylon PA12T80 parts, 5130L10 parts of liquid crystal polymer, 15 parts of HNTs nanotubes, 0.2 part of maleic anhydride, 0.3 part of lubricant, wherein in The mixture of lubricant paraffin and external lubricant silica, the two ratio are 1:1,0.2 part of antioxidant, wherein antioxidant are four [β-（3,5- di-tert-butyl-hydroxy phenyls）Propionic acid] pentaerythritol ester；Preparation method is：
（1）First by high temperature resistant nylon resin, liquid crystal polymer and halloysite nanotubes respectively at 120 DEG C, 140 DEG C and 90 DEG C Forced air drying 10 hours；
（2）Using homogenizer to lubricant, antioxidant and compatilizer carry out mixed at high speed after, be put into drying box into Row drying, drying temperature are 90 DEG C, and drying time is 3 hours；
（3）By step（1）（2）The raw material handled well is put into high-speed mixer, and 5min is uniformly mixed；
（4）By step（3）In the raw material that mixes put into the loading hopper of double screw extruder, through melting extrusion, make Grain；The temperature of each section of double screw extruder is set as：One 280 DEG C of area's temperature, two 285 DEG C of area's temperature, three 285 DEG C of area's temperature, four 295 DEG C of area's temperature, five 285 DEG C of area's temperature, six 290 DEG C of area's temperature, seven 295 DEG C of area's temperature, eight 295 DEG C of area's temperature, nine area's temperature 290 DEG C, ten 290 DEG C of area's temperature, head temperature is 295 DEG C, 350 revs/min of screw speed.One prepared by above-described embodiment Kind of HPN/TLCP/HNTs nanometer tube composite materials, all have excellent mechanical property, can be used as and make automobile, electric The materials'use of various heat-resistant antifriction parts in industry, simultaneously because TLCP has extraordinary flame retardant property, the invention institute The flame retardant property of the product of production is significantly larger than the flame retardant property of general material.The specific test data of its performance is listed in the table below 1：
Table 1
Performance Test method Unit Embodiment 1 Embodiment 2 Embodiment 3
Tensile strength ASTM D638 MPa 102 113 127
Bending strength ASTM D790 MPa 198 235 252
Bending modulus ASTM D790 MPa 11756 12876 14697
Izod notch impact strengths ASTM D256 KJ/m2 19 24 29
Heat distortion temperature ISO75-2 ℃ 255 263 274
This hair can be understood and applied the above description of the embodiments is intended to facilitate those skilled in the art It is bright.Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein General Principle is applied in other embodiment without having to go through creative labor.Therefore, the present invention is not limited to implementations here Example, those skilled in the art's announcement according to the present invention, improvement and modification made without departing from the scope of the present invention all should be Within protection scope of the present invention.

Claims (8)

1. a kind of semi-aromatic nylon/thermotropic liquid crystal polymer/halloysite nanotubes composite material, it is characterised in that：Including The component of following parts by weight：
The semi-aromatic nylon is selected from one or more of PA7T, PA8T or PA12T；
The thermotropic liquid crystal polymer is selected from Du Pont 5130L or Polyplastics E130i；
A diameter of 50~100 μm of the halloysite nanotubes；
The compatilizer is selected from one or more of fumaric acid, itaconic acid or glycidyl acrylate；
The preparation method of the semi-aromatic nylon/thermotropic liquid crystal polymer/halloysite nanotubes composite material include with Lower step：
(1), first semi-aromatic nylon, thermotropic liquid crystal polymer, halloysite nanotubes are separately dried；
(2), lubricant, antioxidant and compatilizer are uniformly mixed, it is dry；
(3), the raw material that step (1), step (2) are handled well is uniformly mixed；
(4), the raw material mixed in step (3) is granulated through double screw extruder melting extrusion, obtains the semi-aromatic Buddhist nun Dragon/thermotropic liquid crystal polymer/halloysite nanotubes composite material；
In the step (1), semi-aromatic nylon, thermotropic liquid crystal polymer and halloysite nanotubes are respectively at 120~130 DEG C, 140~150 DEG C and 90~100 DEG C of forced air dryings 8~10 hours；
In the step (2), after carrying out mixed at high speed to lubricant, antioxidant and compatilizer using homogenizer, it is put into It is dried in drying box, drying temperature is 90~100 DEG C, and drying time is 1~3 hour.
2. semi-aromatic nylon/thermotropic liquid crystal polymer/halloysite nanotubes composite material according to claim 1, It is characterized in that：The lubricant includes one or more of in-lubricant or external lubricant.
3. semi-aromatic nylon/thermotropic liquid crystal polymer/halloysite nanotubes composite material according to claim 2, It is characterized in that：The in-lubricant is selected from fatty acid amide series lubricant agent or hydrocarbon lubricants, wherein fatty acid acyl amine Lubricant is selected from N, the bis- ethylene hard fatty acids amides of N '-, stearic amide or oleamide；The hydrocarbon lubricants are selected from stone Wax, polyethylene wax or polypropylene wax.
4. semi-aromatic nylon/thermotropic liquid crystal polymer/halloysite nanotubes composite material according to claim 2, It is characterized in that：The external lubricant is selected from siloxanes, silica or diatomite.
5. semi-aromatic nylon/thermotropic liquid crystal polymer/halloysite nanotubes composite material according to claim 1, It is characterized in that：The antioxidant is phenols high-temperature antioxidant, is selected from four [β-(3,5- di-tert-butyl-hydroxy phenyl) third Acid] pentaerythritol ester, β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid n-octadecyl alcohol esters or (the 4- tertiary butyls-of 1,3,5- tri- One or more of 3- hydroxyl -2,6- dimethyl benzyls) -1,3,5- triazines -2,4,6- (1H, 3H, 5H)-triketone.
6. a kind of according to claim 1-5 any one of them semi-aromatic nylon/thermotropic liquid crystal polymer/galapectite nanometer The preparation method of pipe composite material, it is characterised in that：Include the following steps：
(1), first semi-aromatic nylon, thermotropic liquid crystal polymer, halloysite nanotubes are separately dried；
(2), lubricant, antioxidant and compatilizer are uniformly mixed, it is dry；
(3), the raw material that step (1), step (2) are handled well is uniformly mixed；
(4), the raw material mixed in step (3) is granulated through double screw extruder melting extrusion, obtains the semi-aromatic Buddhist nun Dragon/thermotropic liquid crystal polymer/halloysite nanotubes composite material；
In the step (1), semi-aromatic nylon, thermotropic liquid crystal polymer and halloysite nanotubes are respectively at 120~130 DEG C, 140~150 DEG C and 90~100 DEG C of forced air dryings 8~10 hours；
In the step (2), after carrying out mixed at high speed to lubricant, antioxidant and compatilizer using homogenizer, it is put into It is dried in drying box, drying temperature is 90~100 DEG C, and drying time is 1~3 hour.
7. preparation method according to claim 6, it is characterised in that：In the step (3), incorporation time be 5~ 10min。
8. preparation method according to claim 6, it is characterised in that：In the step (4), double screw extruder it is each Duan Wendu is set as：One area's temperature is 275 ± 10 DEG C, and two area's temperature are 275 ± 10 DEG C, and three area's temperature are 280 ± 10 DEG C, 4th area Temperature is 285 ± 10 DEG C, and five area's temperature are 295 ± 10 DEG C, and six area's temperature are 295 ± 10 DEG C, and seven area's temperature are 295 ± 10 DEG C, Eight area's temperature are 290 ± 10 DEG C, and nine area's temperature are 285 ± 10 DEG C, and ten area's temperature are 285 ± 10 DEG C, and head temperature is 285 ± 10 DEG C, screw speed is 250~350 revs/min.
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