CN106928703A - Coaseries kaolin/PA66T composites and preparation method thereof - Google Patents

Coaseries kaolin/PA66T composites and preparation method thereof Download PDF

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Publication number
CN106928703A
CN106928703A CN201511026781.2A CN201511026781A CN106928703A CN 106928703 A CN106928703 A CN 106928703A CN 201511026781 A CN201511026781 A CN 201511026781A CN 106928703 A CN106928703 A CN 106928703A
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coaseries kaolin
pa66t
kaolin
modified
composites
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杨桂生
柯昌月
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Shanghai Genius Advanced Materials Group Co Ltd
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Shanghai Genius Advanced Materials Group Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06Polyamides derived from polyamines and polycarboxylic acids
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25Component parts, details or accessories; Auxiliary operations
    • B29C48/92Measuring, controlling or regulating
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00Indexing scheme relating to extrusion moulding
    • B29C2948/92Measuring, controlling or regulating
    • B29C2948/92504Controlled parameter
    • B29C2948/9258Velocity
    • B29C2948/9259Angular velocity
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/002Physical properties
    • C08K2201/003Additives being defined by their diameter
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/02Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025Polymer 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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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention provides a kind of Coaseries kaolin/PA66T composites and preparation method thereof, composite includes:60-80 parts of nylon66 fiber T, 10-30 part of modified Coaseries kaolin, 3-8 parts of lubricant and 2-7 parts of antioxidant;Preparation method includes:It is added in the hopper of double screw extruder after 60-80 parts of dry nylon66 fiber T, 10-30 part of dry modified Coaseries kaolin, 3-8 parts of lubricant and 2-7 parts of antioxidant are well mixed, pellet is obtained through the double screw extruder extruding pelletization, Coaseries kaolin/PA66T composites are obtained final product after drying;In composite of the invention, because Coaseries kaolin is strong with the interface binding power of nylon66 fiber T matrixes and can be evenly dispersed in nylon66 fiber T matrixes, so stretching, bending etc. mechanical property be improved significantly, dimensional stability is preferable, thermal deformation is increased substantially and water absorption rate is significantly reduced, preparation method is simple simultaneously, is adapted to industrialized production.

Description

Coaseries kaolin/PA66T composites and preparation method thereof
Technical field
The invention belongs to technical field of polymer materials, it is related to a kind of Coaseries kaolin/PA66T composites and preparation method thereof.
Background technology
Nylon (polyamide, PA) is a kind of thermoplastic engineering plastic, and it has tough wear-resisting, impact resistance, endurance, corrosion resistant The excellent specific property such as erosion and oil resistant, is widely used in the industries such as auto-parts, electronic apparatus, machinery.Both at home and abroad by copolymerization, Blending, filling, enhancing, fire-retardant, molecule be compound etc., and method is researched and developed to nylon, makes it to high performance and Gao Gong The modified new varieties direction of energyization is developed.
Crystalline polymer nylon66 fiber T is a kind of nylon material, there is firm hydrogen bond between its amide group, with higher Crystallinity and fusing point, preferable corrosion resistance, excellent mechanical property and good wearability and self lubricity, extensively should For fields such as automobile, machinery, electronic apparatus, chemical industry.But, pure nylon66 fiber T be still present heat distortion temperature it is relatively low, inhale The shortcomings of aqueous big, poor water resistance, dry state and low temperature impact performance difference, so as to limit its further application.
The content of the invention
It is a primary object of the present invention to provide a kind of Coaseries kaolin/PA66T composites.
It is another object of the present invention to provide a kind of preparation method of above-mentioned Coaseries kaolin/PA66T composites, the preparation Method and step process is simple, is adapted to industrialized production.
To reach above-mentioned purpose, solution of the invention is:
A kind of Coaseries kaolin/PA66T composites, its raw materials for production contains following components and the weight portion of every kind of component is as follows:
Wherein, nylon66 fiber T can be formed by terephthalic acid (TPA), hexamethylene diamine and the common polycondensation of adipic acid.The number of nylon66 fiber T is divided equally Son amount can be 30000-50000, and fusing point can be 300-310 DEG C.
Modified Coaseries kaolin is the Coaseries kaolin that surface is modified by titanate coupling agent, and the weight portion of titanate coupling agent is accounted for With the 1 ± 0.5% of the weight portion of Coaseries kaolin, 1% is preferably accounted for.
The kaolinic particle diameter of modified coal measures can be 300-500 mesh, can also be preferably 360 mesh.
Lubricant can be ethylene acrylic acid co polymer (A-C540A).
Antioxidant can be the compounding of Hinered phenols antioxidant and phosphite ester kind antioxidant, preferably N, N'- pair-(3- (3,5- bis- Tert-butyl-hydroxy phenyl) propiono) hexamethylene diamine (antioxidant 1098) and three [2,4- di-tert-butyl-phenyl] phosphite ester (antioxygens Agent 168) compounding, N, N'- be double-(3- (3,5- di-tert-butyl-hydroxy phenyl) propiono) hexamethylene diamine and three [2,4- di-t-butyls Phenyl] weight ratio of phosphite ester is preferably (0.5-1):1.
A kind of method for preparing above-mentioned Coaseries kaolin/PA66T composites, it comprises the following steps:By 60-80 parts of drying Nylon66 fiber T, 10-30 part of dry modified Coaseries kaolin, 3-8 parts of lubricant and 2-7 parts of antioxidant it is well mixed after add To in the hopper of double screw extruder, pellet is obtained through the double screw extruder extruding pelletization, it is high to obtain final product coal measures after pellet is dried Ridge soil/PA66T composites.
Wherein, dry nylon66 fiber T is vacuum dried at least 10 hours gained by nylon66 fiber T at 80-100 DEG C, and vacuum is 0.088‐0.100MPa。
Dry modified coal measures kleit preparation method comprises the following steps:Titanium is weighed by the 1 ± 0.5% of Coaseries kaolin weight portion Acid esters coupling agent, is surface-treated using titanate coupling agent to Coaseries kaolin, and it is high to obtain dry modified coal measures after drying Ridge soil;Specifically include following steps:
(1) titanate coupling agent, is weighed by the 1 ± 0.5% of Coaseries kaolin weight portion, is 1 according to volume ratio:1 ratio is added Absolute ethyl alcohol, is made into titanate coupling agent solution;
(2), Coaseries kaolin is placed in high-speed mixer and is stirred with 80 ± 5 DEG C of temperature, be while stirring coupled titanate esters Agent solution is lentamente poured into high-speed mixer, and dry modified Coaseries kaolin is obtained after mixed at high speed and drying.
The draw ratio of the main-machine screw of double screw extruder of the invention is (30-50):1, rotating speed is 200-300r/min.Double spiral shells The rotating speed of the feed screw of bar extruder is 10-20r/min.
The extrusion temperature of double screw extruder may range from 295-335 DEG C.
The drying condition of resulting pellet is after double screw extruder extruding pelletization:At least 10 are vacuum dried at 80-100 DEG C Hour, vacuum is 0.088-0.100MPa.
Due to using such scheme, the beneficial effects of the invention are as follows:
It is modified that the present invention uses modified Coaseries kaolin to be filled nylon66 fiber T, and modified Coaseries kaolin is by titanate esters idol The Coaseries kaolin of connection agent surface treatment, on the one hand, Coaseries kaolin is silicate mineral and the organic carbonaceous thing similar to carbon black The mixture of composition, organic carbonaceous thing therein has certain compatibility with nylon66 fiber T;On the other hand, titanate coupling agent In parent can be combined with modified Coaseries kaolin without generator terminal, parent has the generator terminal can be combined with PA66T, so as to enhance Coaseries kaolin With the compatibility of PA66T, its dispersiveness in PA66T is improved, improve Coaseries kaolin and nylon66 fiber T matrix materials Interface binding power, hence it is evident that improve the mechanical properties such as the stretching and bending of PA66T, finally given with preferable size it is steady Heat distortion temperature qualitative, higher and the Coaseries kaolin of relatively low water absorption rate/PA66T composites.
Specific embodiment
The invention provides a kind of Coaseries kaolin/PA66T composites and preparation method thereof.
<Coaseries kaolin/PA66T composites>
A kind of Coaseries kaolin/PA66T composites, its raw materials for production contains following components and the weight portion of every kind of component is as follows:
Wherein, nylon66 fiber T is formed by terephthalic acid (TPA), hexamethylene diamine and the common polycondensation of adipic acid.The equal molecule of number of nylon66 fiber T Amount can be 30000-50000, and fusing point can be 300-310 DEG C.
Modified Coaseries kaolin is the Coaseries kaolin that surface is modified by titanate coupling agent, wherein, the weight of titanate coupling agent Amount part accounts for 1 ± 0.5% with the weight portion of Coaseries kaolin, preferably 1%.The modified kaolinic particle diameter of coal measures can be 300-500 Mesh, preferably 360 mesh.Coaseries kaolin (gangue) is the discarded object of generation in progress of coal mining, is silicate mineral The mixture constituted with the organic carbonaceous thing similar to carbon black.Inventor's discovery, contained organic matter and nylon in Coaseries kaolin 66T has certain compatibility, therefore it is modified to can use Coaseries kaolin to be filled it.
Lubricant is ethylene acrylic acid co polymer (A-C540A).
Antioxidant is the compounding of Hinered phenols antioxidant and phosphite ester kind antioxidant, it may be preferred to be N, N'- couples-(3- (3,5- bis- Tert-butyl-hydroxy phenyl) propiono) hexamethylene diamine (antioxidant 1098) and three [2,4- di-tert-butyl-phenyl] phosphite ester (antioxygens Agent 168) compounding.Wherein, N, N'- pair-(3- (3,5- di-tert-butyl-hydroxy phenyl) propiono) hexamethylene diamine and three [2,4- bis- Tert-butyl-phenyl] phosphite ester weight ratio be (0.5-1):1.
<The preparation method of Coaseries kaolin/PA66T composites>
The preparation method of above-mentioned Coaseries kaolin/PA66T composites comprises the following steps:By 60-80 parts of dry nylon66 fiber T, 10-30 parts of dry modified Coaseries kaolin, 3-8 parts of lubricant and 2-7 parts of antioxidant are added to twin-screw extrusion after being well mixed In the hopper of machine, pellet is obtained through the double screw extruder extruding pelletization, Coaseries kaolin/PA66T is obtained final product after the pellet is dried Composite.
Wherein, dry nylon66 fiber T is vacuum dried at least 10 hours gained by nylon66 fiber T at 80-100 DEG C, and vacuum is 0.088‐0.100MPa。
Dry modified coal measures kleit preparation method may include steps of:By 1 ± 0.5% title of Coaseries kaolin weight portion Titanate coupling agent is taken, Coaseries kaolin is surface-treated using titanate coupling agent, dry modified coal is obtained after drying It is kaolin, it is specific as follows:
(1) titanate coupling agent, is weighed by the 1 ± 0.5% of Coaseries kaolin weight portion, is 1 according to volume ratio:1 ratio is added (i.e. titanate coupling agent and the volume ratio of absolute ethyl alcohol is 1 to absolute ethyl alcohol:1), it is made into titanate coupling agent solution;
(2), Coaseries kaolin is placed in high-speed mixer and is stirred with 80 ± 5 DEG C of temperature, be while stirring coupled titanate esters Agent solution is lentamente poured into high-speed mixer, mixed at high speed 10min, and dry modified Coaseries kaolin is obtained after drying.Its In, in step (2), dry condition is that at least 4 hours are dried in 120 DEG C of baking oven.
The draw ratio of the main-machine screw of double screw extruder of the invention can be (30-50):1, rotating speed is 200-300r/min, The rotating speed of feed screw can be 10-20r/min.
The extrusion temperature of double screw extruder using zone temperature control, wherein, area's temperature can be 295-305 DEG C, two area's temperature Degree can be 300-310 DEG C, and three area's temperature can be 305-315 DEG C, and four area's temperature can be 310-320 DEG C, and five area's temperature can Think 315-325 DEG C, six area's temperature can be 320-330 DEG C, and head temperature is 325-335 DEG C.Should ensure that temperature from an area to Head gradually rises, i.e. head temperature>Six area's temperature>Five area's temperature>Four area's temperature>Three area's temperature>Two area's temperature>One area's temperature, Preferably ,+5 DEG C of head temperature=six area temperature, six+5 DEG C of temperature=five area of area temperature, five+5 DEG C of temperature=tetra- area of area temperature, 4th area + 5 DEG C of temperature=tri- area temperature, three+5 DEG C of temperature=bis- area of area temperature, two+5 DEG C of temperature=mono- area of area temperature.
The drying condition of the pellet that double screw extruder is extruded is to be vacuum dried at 80-100 DEG C at least 10 hours, and vacuum is 0.088‐0.100MPa。
Coaseries kaolin/nylon66 fiber T composites can be as follows in injection moulding on injection machine, Shooting Technique:Injection temperature scope Can be:310‐340℃;Injection moulding speed can be:10‐15g/s;Injection pressure can be:60‐90MPa;Cool time can Think:20‐30S;The standard batten for correlated performance test can be obtained after injection, is placed 24 hours under the conditions of constant temperature and humidity More than, then can carry out correlated performance test.
The present invention is further illustrated with reference to embodiments.
The method of testing that the present invention is used is as follows:
(1), tensile property:Tested by ASTM D638-10, rate of extension 5mm/min, under constant temperature and humidity experiment condition Test.
(2), simply supported beam notch impact strength:Tested by ASTM D6110-10.
(3), bending strength:Tested by ASTM D790-10, speed 1.25mm/min is pushed, in constant temperature and humidity experiment condition Lower test.
(4), heat distortion temperature:Tested by ASTM D648-07.
(5), water imbibition test:At room temperature, sample is placed in drier, drier bottom is placed one and fills saturated common salt The beaker of the aqueous solution, it is 75% to maintain relative humidity in drier, often crosses 24h taking-up samples and weighs, and is designated as Gi, (i=1,2, 3,4 ...) sample after, weighing still is put back in drier.After 20 days, sample is put into drying in oven (70 DEG C, 24h), then It is placed in drier and is cooled to room temperature weighing sample, is designated as G0.Press the water content (W during formula calculates samplei) %, wherein originally Water absorption rate in invention unanimously calculate 5 days after (120h) water absorption rate:
Wi=(Gi‐G0)/Gi× 100%.
Embodiment one
The processing gross weight of Coaseries kaolin/PA66T composites is 3kg in the present embodiment, and each component content is as shown in table 1.
The constituent content table of the Coaseries kaolin/PA66T composites of the embodiment one of table 1
Wherein, the Coaseries kaolin that is modified is the Coaseries kaolin that surface is modified by titanate coupling agent, the weight of titanate coupling agent Amount part accounts for 1% with the weight portion of Coaseries kaolin.
The preparation method of Coaseries kaolin/PA66T composites comprises the following steps in the present embodiment:
(1), nylon66 fiber T is placed in vacuum drying chamber (temperature is 100 DEG C, and vacuum is 0.088MPa) and is dried 12 hours Fully to remove wherein moisture, dry nylon66 fiber T is obtained;
(2), dry nylon66 fiber T, antioxidant, lubricant and modified Coaseries kaolin are added according to the ratio shown in table 1 It is well mixed in high-speed mixer, obtains pre-composition;
(3), pre-composition is added in double screw extruder, through double screw extruder extruding pelletization, pellet is obtained;This pair of spiral shell The draw ratio of the main-machine screw of bar extruder is 30:1, rotating speed is 200r/min, and the rotating speed of feed screw is 10r/min, extrusion temperature The areas of Du Cong mono- to head is respectively 295 DEG C, 300 DEG C, 305 DEG C, 310 DEG C, 315 DEG C, 320 DEG C and 325 DEG C;
(4) pellet, is vacuum dried 18h in baking oven (temperature is 80 DEG C, and vacuum is 0.1MPa), the present embodiment is obtained Coaseries kaolin/PA66T composites.
By the Coaseries kaolin of the present embodiment/PA66T composites in injection moulding on injection machine, injection temperature it is interval for 310 DEG C, 320 DEG C, 315 DEG C, injection speed is 10g/s, and injection pressure is 60MPa, and cool time is 20S, is obtained for correlated performance The batten of test, the detailed performance of the batten is as shown in table 4.
Embodiment two
The processing gross weight of Coaseries kaolin/PA66T composites is 3kg in the present embodiment, and each component content is as shown in table 2.
The constituent content table of the Coaseries kaolin/PA66T composites of the embodiment two of table 2
Component Content Constitutive property
Nylon66 fiber T 70 weight portions Number-average molecular weight 40000,305 DEG C of fusing point
Modified Coaseries kaolin 20 weight portions The mesh of particle diameter 360
Lubricant 5 weight portions Ethylene acrylic acid co polymer A-C540A
Antioxidant 5 weight portions Antioxidant 1098:Irgasfos 168=0.7:1
Wherein, the Coaseries kaolin that is modified is the Coaseries kaolin that surface is modified by titanate coupling agent, the weight of titanate coupling agent Amount part accounts for 1% with the weight portion of Coaseries kaolin.
The preparation method of Coaseries kaolin/PA66T composites comprises the following steps in the present embodiment:
(1), nylon66 fiber T is placed in vacuum drying chamber (temperature be 90 DEG C, vacuum is 0.1MPa) dry 14 hours with Wherein moisture is fully removed, dry nylon66 fiber T is obtained;
(2), dry nylon66 fiber T, antioxidant, lubricant and modified Coaseries kaolin are added according to the ratio shown in table 2 It is well mixed in high-speed mixer, obtains pre-composition;
(3), pre-composition is added in double screw extruder, through double screw extruder extruding pelletization, pellet is obtained;This pair of spiral shell The draw ratio of the main-machine screw of bar extruder is 40:1, rotating speed is 250r/min, and the rotating speed of feed screw is 15r/min, extrusion temperature The areas of Du Cong mono- to head is respectively 300 DEG C, 305 DEG C, 310 DEG C, 315 DEG C, 320 DEG C, 325 DEG C and 330 DEG C;
(4) pellet, is vacuum dried 15h in baking oven (temperature is 90 DEG C, and vacuum is 0.09MPa), this implementation is obtained Coaseries kaolin/PA66T the composites of example.
By the Coaseries kaolin of the present embodiment/PA66T composites in injection moulding on injection machine, injection temperature it is interval for 325 DEG C, 335 DEG C, 330 DEG C, injection speed is 12g/s, and injection pressure is 75MPa, and cool time is 25S, is obtained for correlated performance The batten of test, the detailed performance of the batten is as shown in table 4.
Embodiment three
The processing gross weight of Coaseries kaolin/PA66T composites is 3kg in the present embodiment, and each component content is as shown in table 3.
The constituent content table of the Coaseries kaolin/PA66T composites of the embodiment three of table 3
Component Content Constitutive property
Nylon66 fiber T 60 weight portions Number-average molecular weight 50000,310 DEG C of fusing point
Modified Coaseries kaolin 30 weight portions The mesh of particle diameter 500
Lubricant 8 weight portions Ethylene acrylic acid co polymer A-C540A
Antioxidant 2 weight portions Antioxidant 1098:Irgasfos 168=1:1
Wherein, the Coaseries kaolin that is modified is the Coaseries kaolin that surface is modified by titanate coupling agent, the weight of titanate coupling agent Amount part accounts for 1% with the weight portion of Coaseries kaolin.
The preparation method of Coaseries kaolin/PA66T composites comprises the following steps in the present embodiment:
(1), nylon66 fiber T is placed in vacuum drying chamber (temperature be 80 DEG C, vacuum is 0.09MPa) dry 16 hours with Wherein moisture is fully removed, dry nylon66 fiber T is obtained;
(2), dry nylon66 fiber T, antioxidant, lubricant and modified Coaseries kaolin are added according to the ratio shown in table 3 It is well mixed in high-speed mixer, obtains pre-composition;
(3), pre-composition is added in double screw extruder, through double screw extruder extruding pelletization, pellet is obtained;This pair of spiral shell The draw ratio of the main-machine screw of bar extruder is 50:1, rotating speed is 300r/min, and the rotating speed of feed screw is 20r/min, extrusion temperature The areas of Du Cong mono- to head is respectively 305 DEG C, 310 DEG C, 315 DEG C, 320 DEG C, 325 DEG C, 330 DEG C and 335 DEG C;
(4) pellet, is vacuum dried 12h in baking oven (temperature is 100 DEG C, and vacuum is 0.088MPa), this reality is obtained Apply the Coaseries kaolin/PA66T composites of example.
By the Coaseries kaolin of the present embodiment/PA66T composites in injection moulding on injection machine, injection temperature it is interval for 330 DEG C, 340 DEG C, 335 DEG C, injection speed is 15g/s, and injection pressure is 90MPa, and cool time is 30S, is obtained for correlated performance The batten of test, the detailed performance of the batten is as shown in table 4.
Comparative example one
By pure nylon66 fiber T pellets in 100 DEG C, vacuum is that 15 hours are dried in 0.10MPa baking ovens after being molded on injection machine Type, it is 310 DEG C, 320 DEG C, 315 DEG C that injection temperature is interval, and injection speed is 15g/s, and injection pressure is 80MPa, during cooling Between be 30S, obtain the batten for correlated performance test, and be compared with embodiment one to three, detailed performance is shown in Table 4.
Comparative example two
By pure nylon66 fiber T pellets in 100 DEG C, to be dried 15 hours in 0.10MPa baking ovens, addition accounts for nylon66 fiber T weights to vacuum The Coaseries kaolin (mesh of particle diameter 360) of the long time without surface modification of part 20% is measured, the two is well mixed after extruding pelletization on extruder, Then injection moulding is carried out, it is 310 DEG C, 320 DEG C, 315 DEG C that injection temperature is interval, and injection speed is 15g/s, and injection pressure is 85MPa, cool time is 25S, obtains the batten for correlated performance test, and be compared with embodiment three, detailed performance It is shown in Table 4.
The performance test results of the composite that above-described embodiment and comparative example are obtained are as shown in table 4:
The performance test table of the composite that the embodiments of the invention of table 4 and comparative example are obtained
Embodiment shown in table 4 and the product test result of comparative example are compared as can be seen that surface treated coal measures is high After ridge soil (modified Coaseries kaolin) adds, on the premise of ensuring that impact strength does not decline to a great extent substantially, the stretching of product is strong Degree, bending strength and heat distortion temperature etc. obtain significantly being lifted very much, illustrate that modified Coaseries kaolin serves increasing well Potent fruit.
Comparative example two and comparative example two are as can be seen that the modified enhancing of Coaseries kaolin and unmodified Coaseries kaolin to product Effect difference is larger, and this demonstrates Coaseries kaolin (the i.e. modified coal series kaolin processed by titanate coupling agent to a certain extent Soil) there is more preferable compatibility with resin matrix, more preferable enhancing effect can be played.
It can also be seen that PA66T is after the Coaseries kaolin enhancing that is modified from the data of table 4, resulting Coaseries kaolin The water absorption rate of/PA66T composites is substantially reduced, and water resistance is substantially improved, and is conducive to keeping good in environment use Dimensional stability.
Inventor has found that Coaseries kaolin is in itself rigid particles, and size is smaller, and surface can be higher, and easy autohemagglutination itself is agglomerating, If directly mixing with PA66T, a large amount of " cluster " structures occur in Coaseries kaolin/PA66T compound systems, so as to influence Its mechanical property, thus compound system impact strength not as good as pure PA66T, but Coaseries kaolin is processed using titanate coupling agent Afterwards, the impact strength of compound system is relative increases.Understood according to coupling mechanism, the parent in coupling agent can be high with coal measures without generator terminal Ridge soil is combined, and parent has the generator terminal can be combined with PA66T, so that it is high with coal measures to form a unified entirety, the i.e. end group of coupling agent two Ridge soil and PA66T carry out chemical coupling or physical entanglement, increased the compatibility of Coaseries kaolin and PA66T.In addition, through idol After connection agent treatment, the surface energy of Coaseries kaolin is not only significantly reduced, reduce the agglomerating phenomenon of its autohemagglutination, and coupling agent point Sub- end group is carbochain more long, Coaseries kaolin is matched with PA66T in polarity, therefore using after coupling agent surface treatment Coaseries kaolin dispersiveness in PA66T is substantially improved, so that when this compound system is subject to outer force deformation, rigid coal series kaolin Grogs can hinder Crack Extension or passivation to terminate crackle, that is, produce pinning effect, and then it is curved to improve the stretching of compound system The performances such as song.
By the implementation process and testing result of each embodiment, it is known that 10-30 parts of modified Coaseries kaolin is added to 60-80 by the present invention The composite obtained in part nylon66 fiber T resins, it has preferable mechanical property and water resistance, while heat distortion temperature is significantly Degree is improved, so that the dimensional stability of composite improves.
The above-mentioned description to embodiment is to be understood that and use the present invention for ease of those skilled in the art.It is familiar with The personnel of art technology obviously can easily make various modifications to these embodiments, and should General Principle described herein Use in other embodiment without by performing creative labour.Therefore, the invention is not restricted to above-described embodiment, art technology Personnel's announcement of the invention, does not depart from improvement that scope made and modification all should be in protection scope of the present invention Within.

Claims (9)

1. a kind of Coaseries kaolin/PA66T composites, it is characterised in that:Its raw materials for production contains following components and every kind of component Weight portion it is as follows:
2. Coaseries kaolin according to claim 1/PA66T composites, it is characterised in that:The nylon66 fiber T is by benzene Dioctyl phthalate, hexamethylene diamine and the common polycondensation of adipic acid are formed;
Preferably, the number-average molecular weight of the nylon66 fiber T is 30000-50000;And/or, the fusing point of the nylon66 fiber T is 300‐310℃。
3. Coaseries kaolin according to claim 1/PA66T composites, it is characterised in that:The modified Coaseries kaolin Particle diameter be 300-500 mesh;And/or, the modified Coaseries kaolin is the coal series kaolin that surface is modified by titanate coupling agent Soil;
Preferably, the modified Coaseries kaolin particle diameter is 360 mesh;And/or, in the modified Coaseries kaolin, the titanium The weight portion of acid esters coupling agent accounts for 1 ± 0.5% with the weight portion of the Coaseries kaolin.
4. Coaseries kaolin according to claim 1/PA66T composites, it is characterised in that:The lubricant is ethylene propylene Olefin(e) acid copolymer (A-C540A);And/or,
The antioxidant is the compounding of Hinered phenols antioxidant and phosphite ester kind antioxidant;
Preferably, the antioxidant is N, N'- couples-(3- (3,5- di-tert-butyl-hydroxy phenyl) propiono) hexamethylene diamine (antioxidant 1098) with the compounding of three [2,4- di-tert-butyl-phenyl] phosphite ester (irgasfos 168s);
It is highly preferred that N, N'- pair-(3- (3,5- di-tert-butyl-hydroxy phenyl) propiono) hexamethylene diamine and three [2,4- di-tert-butyls Base] phosphite ester weight ratio be (0.5-1):1.
5. a kind of method of the Coaseries kaolin/PA66T composites prepared as described in any in Claims 1-4, its feature exists In comprising the following steps:By 60-80 parts of dry nylon66 fiber T, 10-30 part of dry modified Coaseries kaolin, 3-8 parts of profit It is added in the hopper of double screw extruder after lubrication prescription and 2-7 parts of antioxidant are well mixed, through the double screw extruder extruding pelletization Pellet is obtained, Coaseries kaolin/PA66T composites are obtained final product after the pellet is dried.
6. method according to claim 5, it is characterised in that:The dry modified coal measures kleit preparation method includes Following steps:Titanate coupling agent is weighed by the 1 ± 0.5% of Coaseries kaolin weight portion, using the titanate coupling agent to described Coaseries kaolin is surface-treated, and the dry modified Coaseries kaolin is obtained after drying.
7. method according to claim 5, it is characterised in that:The dry modified coal measures kleit preparation method includes Following steps:
(1) titanate coupling agent, is weighed by the 1 ± 0.5% of Coaseries kaolin weight portion, is 1 according to volume ratio:1 ratio is added Absolute ethyl alcohol, is made into titanate coupling agent solution;
(2), Coaseries kaolin is placed in high-speed mixer and is stirred with 80 ± 5 DEG C of temperature, while stirring by the titanate esters Coupling agent solution is lentamente poured into the high-speed mixer, and the dry modified coal series kaolin is obtained after mixed at high speed and drying Soil.
8. method according to claim 5, it is characterised in that:The draw ratio of the main-machine screw of the double screw extruder is (30‐50):1;And/or,
The main-machine screw rotating speed of the double screw extruder is 200-300r/min;And/or,
The rotating speed of the feed screw of the double screw extruder is 10-20r/min.
9. method according to claim 5, it is characterised in that:The pellet is vacuum dried at least 10 hours at 80-100 DEG C, Vacuum is 0.088-0.100MPa;And/or,
The dry nylon66 fiber T is vacuum dried at least 10 hours gained by nylon66 fiber T at 80-100 DEG C, and vacuum is 0.088‐0.100MPa。
CN201511026781.2A 2015-12-31 2015-12-31 Coaseries kaolin/PA66T composites and preparation method thereof Pending CN106928703A (en)

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CN109251515A (en) * 2018-09-07 2019-01-22 山西琚丰新材料科技有限公司 A kind of preparation method of PA kaolin composite material
CN109867854A (en) * 2019-03-22 2019-06-11 福建凯达集团有限公司 High-strength polyethylene microporous membrane and preparation method thereof

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CN103709794A (en) * 2014-01-15 2014-04-09 郭凯 Method for preparing modified calcined coal kaolin for rubber by employing solution method
CN104004274A (en) * 2014-05-07 2014-08-27 安徽博源自动化仪表有限公司 High temperature-resistant aging-resistant electro-insulating rubber material for instrument element
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CN104419201A (en) * 2013-08-23 2015-03-18 上海杰事杰新材料(集团)股份有限公司 Vermiculite filled nylon 66 T material and preparation method thereof
CN103694747A (en) * 2014-01-15 2014-04-02 郭凯 Method for preparing modified calcined coal kaolin for rubber by ball milling process
CN103709794A (en) * 2014-01-15 2014-04-09 郭凯 Method for preparing modified calcined coal kaolin for rubber by employing solution method
CN104004274A (en) * 2014-05-07 2014-08-27 安徽博源自动化仪表有限公司 High temperature-resistant aging-resistant electro-insulating rubber material for instrument element

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* Cited by examiner, † Cited by third party
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