CN106433113A - Semi-aromatic nylon composite material and preparation method thereof - Google Patents
Semi-aromatic nylon composite material and preparation method thereof Download PDFInfo
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- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
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- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
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- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
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- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
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Abstract
A semi-aromatic nylon composite material is prepared by mixing semi-aromatic nylon and flexibilizer. Semi-aromatic nylon is prepared through a polymerization reaction from a mixture of binary acid and diamine or nylon composite salt, high-fineness reinforcing filler, an end-capping agent and a catalyst. The flexibilizer is a grafted and modified olefine copolymer, and the grafting rate of the flexibilizer is 0.0005x-0.003x of mass percentage, wherein x is the calculation value of the molar weight of amido bonds contained in 1000 g of semi-aromatic nylon. A preparation method of the semi-aromatic nylon composite material includes the steps that semi-aromatic nylon resin is synthesized; the semi-aromatic nylon resin is mixed with the flexibilizer with a certain grafting rate and a functional auxiliary according to the proportion; the mixture is extruded and formed by a screw extruder, and the semi-aromatic nylon composite material is prepared. Problems about impact performance and warping of semi-aromatic nylon can be effectively improved, and meanwhile influences on tensile properties, bending performance and thermal deformation temperature of semi-aromatic nylon are small.
Description
Technical field
The invention belongs to macromolecular material and its preparing technical field, more particularly, to a kind of nylon-type composite and preparation method thereof.
Background technology
Fatty polyamide (as nylon 6, nylon66 fiber) has excellent mechanical strength, chemical-resistant, wearability and Zi Run
Slip, application is related to electronic apparatus, automobile component, fiber dress ornament, is one of current most important in the world engineering plastics.
Semi-aromatic nylon is a kind of polyamides being obtained through copolymerization with aliphatic diamine or diacid by the binary acid with aromatic rings or diamine
Amine material, possesses the workability of amorphous nylon, and intensity, heat-resisting, solvent resistant, hygroscopicity and dimensional stability are better than simultaneously
Common fats race nylon.Various processing and forming mode is with excellent performance so as to can be suitably used for some amorphous nylon and virtue entirely
Race's nylon all cannot meet the field of requirement, such as the lightweight of automotive engine component, the surface mounting technique of electronic device.Mesh
Before, main semi-aromatic nylon product has：Nylon 6T copolymer, nylon 9 T, nylon 10T etc..Wherein nylon 6T copolymerization
Thing is obtained with other amorphous nylon salt copolymerization by nylon 6T salt, due to can obtain a series of differences by changing each material content
The product of performance is to meet different application requirements, and its raw material is easy to get relatively, and nylon 6T copolymer is in existing semi-aromatic nylon
The ratio of maximum is occupied in product.
US4603166, US4603193, US4831108, US4163101, US5387645, US5112685, US5153250,
US5500473, US5981692, US5516882 United States Patent (USP) and CN103360598A, CN102477219A,
CN1127266A、CN1537881A、CN1127266A、CN1246490A、CN1227232A、CN103923313A
The synthetically produced method of various different semi-aromatic nylons is disclosed, these methods are complementary to one another, further in Chinese patent literature
The perfect manufacturing process of semi-aromatic nylon resin.
As a kind of engineering plastics, it possesses good stretching, bending property to semi-aromatic nylon, higher heat distortion temperature with excellent
Different dimensional stability, however, simple semi-aromatic nylon resin exists, impact property is poor, the defect of the easy warpage of injection-molded item,
Typically require and improve its impact property by adding toughener.
Conventional plastics toughening agent is mainly elastomer substances, such as ABS (acrylonitrile-butadiene-styrene copolymer), SBS (benzene
Ethylene-butadiene-styrene copolymer), the non-polar polymer such as POE (ethylene-octene copolymer), in modified polar polymer
During semi-aromatic nylon, both poor compatibility and there is sharp interface, toughening effect is not good；This also leads to the stretching of material, bending
And thermal deformation behavior declines to a great extent.By the graft (as maleic anhydride, metering system ethylene oxidic ester) with active group
Graft modification toughener, can increase the compatibility of toughener and semi-aromatic nylon.
CN102617850A Chinese patent literature discloses a kind of nylon composite materials with good fracture toughness and its preparation
Method, the method is prepared for the big modification of nylon material of initial impact energy of rupture by adding ethylene-octene copolymer as toughener
Material, but used in the method, ethylene-octene copolymer is non-modified, is applied to polar polymer nylon as non-polar polymer
In, both poor compatibility, toughening effect is limited, and other hydraulic performance declines are obvious.
CN103834161A Chinese patent literature discloses a kind of basalt fibre, graft modification toughener jointly modified half
Aramid fiber composite and preparation method thereof, the method discloses basalt fibre and semi-aromatic nylon composite property is carried
Ascending effect, but do not disclose the effect of graft modification toughener comprehensively, also restriction is not made to the percent grafting of toughener, and mistake
High or too low percent grafting all can adversely affect to toughening effect.Percent grafting refers to the mass ratio of grafting material and graft product,
Ethylene-octene copolymer as direct in maleic anhydride, graft is maleic anhydride, graft product is the direct ethylene-octene of maleic anhydride
Copolymer；Percent grafting is too low, limited to both Compatibility improvements, and percent grafting is too high, reacts to each other between the graft on toughener,
Equally it is unfavorable for the improvement of toughening effect, significantly affect other performances of semi-aromatic nylon simultaneously.
On the other hand, in order to tackle nylon products warpage issues, generally pass through to add inorganic reinforcing filler for example glass, barium sulfate,
Glass microballoon etc. is blended with nylon resin.CN104031384 Chinese patent literature discloses one kind and prepares high glaze low-warpage nylon
The method of imperial 66 materials, the method uses nano barium sulfate, dispersant, antioxidant, nucleator, blending and modifying nylon66 fiber,
Disclose nano barium sulfate as reinforcer more preferable dispersion effect in the base.CN 102888100A Chinese patent literature
Disclose a kind of Halogen warpage preventing deformation reinforced nylon 6 and its preparation technology, the method uses glass, glass microballoon to strengthen nylon
6.The large usage quantity of inorganic filler in said method, packing quality accounts for the 30% of composite quality.
When needing to be simultaneously introduced substantial amounts of toughener and inorganic filler to improve the shock resistance of material with warpage situation, too high
Amount of filler and toughener and inorganic filler incompatibility, the properties of material can be had a strong impact on, and then lead to material
Bending, stretching, shock resistance decline comprehensively, also result in the increase of the process costs of material.
Content of the invention
The technical problem to be solved is to overcome the toughener mentioned in background above technology and the semi-aromatic nylon compatibility
Bad, toughener and inorganic filler consumption are higher, the problems such as lead to material property to decline, to provide one kind to be effectively improved half comprehensively
Aramid fiber impact property and warpage issues, affect less simultaneously on the stretching of semi-aromatic nylon, bending property and heat distortion temperature
Semi-aromatic nylon composite with and preparation method thereof.
For solving above-mentioned technical problem, technical scheme proposed by the present invention is a kind of semi-aromatic nylon composite, described semiaromatic
Nylon composite materials are mainly formed by the component mixed preparing of following mass fraction：
100 parts of semi-aromatic nylon；
2～50 parts of toughener；
Described semi-aromatic nylon is mainly prepared by after the aggregated reaction of raw material of following mass fraction：
The mixing of binary acid A and diamine A, or 100 parts of nylon complex salt A；
The mixing of binary acid B and diamine B, or 70～250 parts of nylon complex salt B；
8～35 parts of high fineness reinforcer,
1.5～22 parts of end-capping reagent, and
0.2～0.4 part of catalyst (preferably hypophosphite)；
Described toughener is the olefinic copolymer after graft modification, and the percent grafting of toughener is 0.0005x～0.003x matter
Amount fraction；Wherein；X is the value of calculation of the amido link mole contained by semi-aromatic nylon described in 1000g.
It is preferred that described binary acid A is p-phthalic acid in above-mentioned semi-aromatic nylon composite, described diamine A is
One of hexamethylene diamine, nonamethylene diamine, decamethylene diamine, 12 carbon diamines, 13 carbon diamines.It is furthermore preferred that described diamine
A is hexamethylene diamine, nonamethylene diamine or decamethylene diamine.Described nylon complex salt A is the reaction product of binary acid A and diamine A.
It is preferred that described binary acid B is M-phthalic acid, adipic acid, decanedioic acid in above-mentioned semi-aromatic nylon composite
Or SL-AH, described diamine B is hexamethylene diamine, nonamethylene diamine, decamethylene diamine, 12 carbon diamines, 13 carbon diamines
One of.Described nylon complex salt B is the reaction product of binary acid B and diamine B or is in caprolactam or 12
Amide, more preferably M-phthalic acid-hexamethylene diamine complex salt, M-phthalic acid-nonamethylene diamine complex salt, M-phthalic acid-decamethylene diamine
Complex salt, M-phthalic acid-ten two carbon diamine complex salt, M-phthalic acid-ten three carbon diamine complex salt, adipic acid-oneself two
Amine complex salt, caprolactam, decanedioic acid-hexamethylene diamine complex salt, SL-AH-hexamethylene diamine complex salt, decanedioic acid-decamethylene diamine
One or more of complex salt, SL-AH-ten two carbon diamine complex salt, lauric lactam；Particularly preferably isophthalic
Dioctyl phthalate-hexamethylene diamine complex salt, adipic acid-hexamethylene diamine complex salt, caprolactam or lauric lactam.
It is preferred that described high fineness reinforcer is nano barium sulfate, nano-talc in above-mentioned semi-aromatic nylon composite
One of powder, nanometer wollastonite, nano mica powder, glass microballoon.It is furthermore preferred that described high fineness reinforcer is nanometer
Barium sulfate or glass microballoon.
In above-mentioned semi-aromatic nylon composite it is preferred that described end-capping reagent be benzoic acid, 2- naphthoic acid, in 2- naphthalene acetic acid
One kind.
It is preferred that described catalyst is ortho phosphorous acid potassium, sodium hypophosphite, secondary Asia in above-mentioned semi-aromatic nylon composite
One of magnesium phosphate, Lime Hypophosphate, ortho phosphorous acid zinc.
In above-mentioned semi-aromatic nylon composite it is preferred that described toughener be maleic anhydride grafted ethene-octene copolymer,
Maleic anhydride grafting EP rubbers, glycidyl methacrylate graft ethylene-octene copolymer or styrene-butadiene-benzene second
Alkene block copolymer.It is furthermore preferred that the percent grafting of described maleic anhydride grafted ethene-octene copolymer is 0.0005x～0.003x
Mass fraction；The percent grafting of described glycidyl methacrylate graft ethylene-octene copolymer is 0.0005x～0.003x；
X therein is the value of calculation of the amido link mole contained by semi-aromatic nylon described in 1000g.Described toughener is more preferably horse
Maleic anhydride grafted ethylene-octene copolymer or glycidyl methacrylate graft ethylene-octene copolymer.
The technique scheme of the present invention is based primarily upon following thinking：Fill out by the high fineness that adds a small amount of in the course of the polymerization process is inorganic
Material, prepares in-situ polymerization enhanced semi-aromatic nylon resin, reuses the graft modification toughener of particular types, certain percent grafting,
Modified with in-situ polymerization enhanced semi-aromatic nylon resin alloy, to provide one kind to be effectively improved semi-aromatic nylon impact property and stick up
Qu Wenti, affects less semi-aromatic nylon composite to the stretching of semi-aromatic nylon, bending property and heat distortion temperature simultaneously.
Above-mentioned composite-material formula is us through repeatedly obtaining with after substantial amounts of experiment, and final product achieve unexpected
Effect.
As a total technology design, the present invention also provides a kind of preparation method of above-mentioned semi-aromatic nylon composite, including
Following steps：
(1) synthesize semi-aromatic nylon resin：Under the conditions of water does reaction medium, with described binary acid A and diamine A and two
Unit acid B and diamine B is made into binary acid and diamine concentrated solution for raw material, or is combined with nylon with described nylon complex salt A
Salt B is made into nylon saline solution (temperature rises to 150 DEG C～180 DEG C, and solution is concentrated into 50%～90%) for raw material, adds high thin
Degree reinforcer, end-capping reagent and catalyst carry out prepolymerization, control prepolymerization temperature at 180 DEG C～240 DEG C, discharge in concentrated solution
Hydrone, prepolymerization time controls at 0.1～5 hour；Pressure is 0.8～2.5MPa；After the completion of prepolymerization, pressure unloads
To normal pressure, prepolymer is expelled directly out from bottom valve, cooling, is ground into prepolyer granule (granule of preferably 0.5～2mm size)；
Prepolyer granule (is vacuum dried 5～15 hours) after drying preferably at 100 DEG C, carries out under the heating condition that progressively heats up
Solid phase polycondensation, obtains semi-aromatic nylon resin；
(2) prepare semi-aromatic nylon composite：The semi-aromatic nylon resin that be obtained step (1) and the increasing of certain percent grafting
Tough dose, functional aid is mixed in proportion, then carries out extrusion molding, prepared semi-aromatic nylon composite by screw extruder.
In above-mentioned preparation method, preferably：Described binary acid is controlled 70%～90% with the concentration of diamine concentrated solution；In advance
Polymerization temperature controls at 210 DEG C～230 DEG C；Prepolymerization time controlled at 0.5～2 hour.
In above-mentioned preparation method, preferably：Condensation temperature during described solid phase polycondensation is controlled to 170 DEG C～260 DEG C, vacuum
For 1～1000Pa, polycondensation time control is 5～25 hours.
In above-mentioned preparation method, preferably：Described screw extruder is parallel dual-screw extruding machine, this screw extruder
1～9 section of temperature of screw rod is controlled to successively：(y-10)℃、(y-10)℃、(y-5)℃、(y-5)℃、(y)℃、(y+10)℃、(y+20)℃、
(y+10) DEG C, (y) DEG C, y is the fusing point of semi-aromatic nylon resin.The rotating speed of screw extruder is preferably 200r/min.
Compared with prior art, it is an advantage of the current invention that：By adding high fineness reinforcer in polymerization, make filler more preferable
Dispersion in the polymer, compared to extrusion blending, improve the warpage situation of polymer with lower addition, be toughener
Blending consumption leave space.On this basis, by using the enhanced pole of the toughness reinforcing in-situ polymerization of the toughener after graft modification
Property polymer semi-aromatic nylon, increased the compatibility of toughener and polymer, increased toughening effect, decrease bending, draw
Stretch the decline level of performance.In preferred scheme, according to the semi-aromatic nylon institute amide bond molal quantity of unit mass, limit
The percent grafting of toughener, this percent grafting grafting toughening agent within the specific limits both had preferably compatible with semi-aromatic nylon
Property, but not reason percent grafting too high and lead to be grafted active group be cross-linked with each other and to composite property produce counter productive.This
The semi-aromatic nylon composite products of the final preparation of invention have the characteristics that high temperature resistant, high intensity, high tenacity, low warpage, protect
Hold good bending, tensile property and heat distortion temperature, there is good shock resistance.
Specific embodiment
For the ease of understanding the present invention, below in conjunction with preferred embodiment, the present invention is made more comprehensively, meticulously to describe, but this
The protection domain of invention is not limited to embodiment in detail below.
Unless otherwise defined, all technical term used hereinafter is identical with the implication that those skilled in the art are generally understood that.
Technical term used herein is intended merely to describe the purpose of specific embodiment, is not intended to limit the protection model of the present invention
Enclose.
Unless otherwise specified, the various raw materials used in the present invention, reagent, instrument and equipment etc. all can be purchased by market
Can buy or can be prepared by existing method.
Embodiment 1：
A kind of semi-aromatic nylon composite of present invention, it is mainly formed by the component mixed preparing of following mass fraction：
100 parts of semi-aromatic nylon resin；
20 parts of maleic anhydride grafted ethene-octene copolymer (toughener)；
The percent grafting of wherein maleic anhydride grafted ethene-octene copolymer is the 0.73% (amido link of 1000g resin in the present embodiment
Molal quantity x is 7.34,0.73% corresponding 0.001x).
In above-mentioned semi-aromatic nylon composite, semi-aromatic nylon resin is mainly by the aggregated reaction of raw material of following mass fraction
After prepare：
P-phthalic acid -100 parts of hexamethylene diamine complex salt,
Adipic acid -82 parts of hexamethylene diamine complex salt,
Nanometer wollastonite (200nm<D50<800nm) 9 parts,
5.5 parts of benzoic acid, and
0.22 part of sodium hypophosphite.
The preparation method of the semi-aromatic nylon composite of above-mentioned the present embodiment, specifically includes following steps：
(1) synthesize semi-aromatic nylon resin：
Under the conditions of water does reaction medium, it is combined with 100 parts of p-phthalic acids-hexamethylene diamine complex salt and 82 parts of adipic acid-hexamethylene diamines
Salt is made into the nylon saline solution of mass fraction 60% for raw material, concentrates nylon saline solution, obtain 78%～82% under the conditions of 170 DEG C
Binary acid and diamine concentrated solution, add the catalyst of 9 parts of nanometer wollastonites, 5.5 parts of end-capping reagent benzoic acid and 2.2 parts
Sodium phosphite carries out prepolymerization, controls prepolymerization temperature at 210 DEG C～230 DEG C, discharges the hydrone in concentrated solution, during prepolymerization
Between control at 2 hours；Pressure is 1.8～2.0MPa；After the completion of prepolymerization, pressure unloads to normal pressure, and prepolymer is straight from bottom valve
Run in, cooling, it is ground into prepolyer granule (granule of 0.5～2mm size)；Prepolyer granule is through true at 100 DEG C
Empty dry 12 hours, then progressively heat up and carry out solid phase polycondensation, condensation temperature during polycondensation controls 240 DEG C, vacuum is 20Pa,
Polycondensation time control is 14 hours, obtains semi-aromatic nylon resin；
(2) prepare semi-aromatic nylon composite：Semi-aromatic nylon resin 100 mass parts that be obtained step (1) and 20 matter
Amount part percent grafting is 0.73% maleic anhydride grafted ethene-octene copolymer mix homogeneously, adds parallel dual-screw extruding machine hopper,
1～9 section of temperature control of screw rod is 285 DEG C, 285 DEG C, 290 DEG C, 290 DEG C, 295 DEG C, 305 DEG C, 315 DEG C, 305 DEG C, 295 DEG C,
Rotating speed is 200r/min, carries out extrusion molding, prepared semi-aromatic nylon composite by screw extruder.
Comparative example 1：
A kind of preparation method of semi-aromatic nylon composite, specifically includes following steps：
(1) this step synthesizes the operation of semi-aromatic nylon resin and the technological operation phase of synthesis semi-aromatic nylon resin in embodiment 1
With；
(2) prepare semi-aromatic nylon composite：Semi-aromatic nylon resin 100 mass parts that be obtained step (1) and 20 matter
Amount part, without the ethylene-octene copolymer mix homogeneously of graft modification, adds parallel dual-screw extruding machine hopper, 1～9 section of screw rod
Temperature control is 285 DEG C, 285 DEG C, 290 DEG C, 290 DEG C, 295 DEG C, 305 DEG C, 315 DEG C, 305 DEG C, 295 DEG C, and rotating speed is
200r/min, carries out extrusion molding, prepared semi-aromatic nylon composite by screw extruder.
As can be seen that using ethylene-octene copolymer (toughener) the modification identical of equivalent from embodiment 1 with comparative example 1
Semi-aromatic nylon resin, ethylene-octene copolymer (toughener) modified effect without grafting is substantially poor, and toughening effect is not good,
Other performances are also decreased obviously, and destroy the effect (ginseng of material without simple the playing of the ethylene-octene copolymer (toughener) of grafting
See table 1).
Embodiment 2：
A kind of semi-aromatic nylon composite of present invention, it is mainly formed by the component mixed preparing of following mass fraction：
100 parts of semi-aromatic nylon resin；
8 parts of maleic anhydride grafted ethene-octene copolymer (toughener)；
The percent grafting of wherein maleic anhydride grafted ethene-octene copolymer is the 1.11% (amido link of 1000g resin in the present embodiment
Molal quantity x is 7.47,1.11% corresponding 0.0015x).
In above-mentioned semi-aromatic nylon composite, semi-aromatic nylon resin is mainly by the aggregated reaction of raw material of following mass fraction
After prepare：
P-phthalic acid -100 parts of hexamethylene diamine complex salt,
Adipic acid -233 parts of hexamethylene diamine complex salt,
Nano barium sulfate (200nm<D50<600nm) 33 parts,
10 parts of benzoic acid, and
0.4 part of sodium hypophosphite.
The preparation method of the semi-aromatic nylon composite of above-mentioned the present embodiment, specifically includes following steps：
(1) synthesize semi-aromatic nylon resin：
Under the conditions of water does reaction medium, multiple with 100 parts of p-phthalic acids-hexamethylene diamine complex salt and 233 parts of adipic acid-hexamethylene diamines
Close salt and be made into the nylon saline solution of mass fraction 70% for raw material, concentration nylon saline solution under the conditions of 170 DEG C, obtain 78%～
82% binary acid and diamine concentrated solution, meanwhile add 33 parts of nano barium sulfates, 10 parts of end-capping reagent benzoic acid and 4
The catalyst sodium hypophosphite of part, controls prepolymerization temperature to carry out prepolymerization at 210 DEG C～230 DEG C, discharges the moisture in concentrated solution
Son, prepolymerization time controlled at 2 hours；Pressure is 1.8～2.0MPa；After the completion of prepolymerization, pressure unloads to normal pressure, in advance
Polymers is expelled directly out from bottom valve, cooling, is ground into prepolyer granule (granule of 0.5～2mm size)；Prepolyer granule passes through
It is vacuum dried at 100 DEG C 12 hours, then progressively heats up and carry out solid phase polycondensation, condensation temperature during polycondensation controls 240 DEG C,
Vacuum is 20Pa, and polycondensation time control is 14 hours, obtains semi-aromatic nylon resin；
(2) prepare semi-aromatic nylon composite：Semi-aromatic nylon resin 100 mass parts that be obtained step (1) and 8 matter
Amount part percent grafting is 1.11% maleic anhydride grafted ethene-octene copolymer mix homogeneously, adds parallel dual-screw extruding machine hopper,
1～9 section of temperature control of screw rod is 275 DEG C, 275 DEG C, 280 DEG C, 280 DEG C, 285 DEG C, 295 DEG C, 305 DEG C, 295 DEG C, 285 DEG C,
Rotating speed is 200r/min, carries out extrusion molding, prepared semi-aromatic nylon composite by screw extruder.
Comparative example 2：
A kind of preparation method of semi-aromatic nylon composite, specifically includes following steps：
(1) this step synthesizes the operation of semi-aromatic nylon resin and the technological operation phase of synthesis semi-aromatic nylon resin in embodiment 2
With；
(2) prepare semi-aromatic nylon composite：Semi-aromatic nylon resin 100 mass parts that be obtained step (1) and 8 matter
Amount part percent grafting is the maleic anhydride grafted ethene-octene copolymer mix homogeneously of 2.5% (corresponding 0.0033x), adds double in the same direction
Screw extruder hopper, 1～9 section of temperature control of screw rod be 275 DEG C, 275 DEG C, 280 DEG C, 280 DEG C, 285 DEG C, 295 DEG C,
305 DEG C, 295 DEG C, 285 DEG C, rotating speed is 200r/min, carries out extrusion molding by screw extruder, and prepared semi-aromatic nylon is multiple
Condensation material.
, compared with comparative example 2, in comparative example 2, toughener percent grafting is too high for embodiment 2, self crosslinked increase of toughener, increases
Tough effect declines a lot (referring to table 1 below).
Embodiment 3：
A kind of semi-aromatic nylon composite of present invention, it is mainly formed by the component mixed preparing of following mass fraction：
100 parts of semi-aromatic nylon resin；With
12 parts of maleic anhydride grafted ethene-octene copolymer (toughener)；
The percent grafting of wherein maleic anhydride grafted ethene-octene copolymer is the 0.62% (amido link of 1000g resin in the present embodiment
Molal quantity x is 6.23,0.62% corresponding 0.001x).
In above-mentioned semi-aromatic nylon composite, semi-aromatic nylon resin is mainly by the aggregated reaction of raw material of following mass fraction
After prepare：
To benzene two-formic acid -100 parts of hexamethylene diamine complex salt,
Decanedioic acid -82 parts of decamethylene diamine complex salt,
(2 μm of glass microballoon<D50<5 μm) 9 parts,
5.5 parts of benzoic acid, and
0.22 part of sodium hypophosphite.
The preparation method of the semi-aromatic nylon composite of above-mentioned the present embodiment, specifically includes following steps：
(1) synthesize semi-aromatic nylon resin：
Under the conditions of water does reaction medium, it is combined with 100 parts of p-phthalic acids-hexamethylene diamine complex salt and 82 parts of decanedioic acid-decamethylene diamines
Salt is made into the nylon saline solution of mass fraction 50% for raw material, concentrates nylon saline solution, obtain 78%～82% under the conditions of 170 DEG C
Binary acid and diamine concentrated solution, meanwhile add urging of 9 parts of glass microballoons, 5.5 parts of end-capping reagent benzoic acid and 2.2 parts
Agent sodium hypophosphite carries out prepolymerization, controls prepolymerization temperature at 210 DEG C～230 DEG C, discharges the hydrone in concentrated solution, in advance
Polymerization time controlled at 2 hours；Pressure is 1.8～2.0MPa；After the completion of prepolymerization, pressure unloads to normal pressure, prepolymer from
Bottom valve is expelled directly out, cooling, is ground into prepolyer granule (granule of 0.5～2mm size)；Prepolyer granule is through at 100 DEG C
Lower vacuum drying 12 hours, then progressively heats up and carries out solid phase polycondensation, and condensation temperature during polycondensation controls 240 DEG C, and vacuum is
20Pa, polycondensation time control is 14 hours, obtains semi-aromatic nylon resin；
(2) prepare semi-aromatic nylon composite：Semi-aromatic nylon resin 100 mass parts that be obtained step (1) and 12 matter
Amount part percent grafting is 0.62% maleic anhydride grafted ethene-octene copolymer mix homogeneously, adds parallel dual-screw extruding machine hopper,
1～9 section of temperature control of screw rod is 290 DEG C, 290 DEG C, 295 DEG C, 295 DEG C, 300 DEG C, 310 DEG C, 320 DEG C, 310 DEG C, 300 DEG C,
Rotating speed is 200r/min, carries out extrusion molding, prepared semi-aromatic nylon composite by screw extruder.
Comparative example 3：
A kind of preparation method of semi-aromatic nylon composite, specifically includes following steps：
(1) this step synthesizes the operation of semi-aromatic nylon resin and the technological operation phase of synthesis semi-aromatic nylon resin in embodiment 3
With；
(2) prepare semi-aromatic nylon composite：Semi-aromatic nylon resin 100 mass parts that be obtained step (1) and 60 matter
Amount part percent grafting is 0.62% maleic anhydride grafted ethene-octene copolymer mix homogeneously, adds parallel dual-screw extruding machine hopper,
1～9 section of temperature control of screw rod is 290 DEG C, 290 DEG C, 295 DEG C, 295 DEG C, 300 DEG C, 310 DEG C, 320 DEG C, 310 DEG C, 300 DEG C,
Rotating speed is 200r/min, carries out extrusion molding, prepared semi-aromatic nylon composite by screw extruder.
, compared with comparative example 3, in comparative example 3, toughener consumption is too high, and toughener defines in the material for embodiment 3
Continuous phase, toughness significantly improves, but has had been out the advantage of semi-aromatic nylon high rigidity, high-fire resistance (referring to following table simultaneously
1).
Embodiment 4：
A kind of semi-aromatic nylon composite of present invention, it is mainly formed by the component mixed preparing of following mass fraction：
100 parts of semi-aromatic nylon resin；
30 parts of glycidyl methacrylate graft ethylene-octene copolymer (toughener)；With
The percent grafting of wherein glycidyl methacrylate graft ethylene-octene copolymer is that 0.71% (the present embodiment is equivalent to
0.001x).
In above-mentioned semi-aromatic nylon composite, semi-aromatic nylon resin is mainly by the aggregated reaction of raw material of following mass fraction
After prepare：
P-phthalic acid -100 parts of hexamethylene diamine complex salt,
M-phthalic acid -70 parts of hexamethylene diamine complex salt,
Nano barium sulfate (200nm<D50<600nm) 8.5 parts,
5 parts of benzoic acid, and
0.2 part of sodium hypophosphite.
The preparation method of the semi-aromatic nylon composite of above-mentioned the present embodiment, specifically includes following steps：
(1) synthesize semi-aromatic nylon resin：
Under the conditions of water does reaction medium, with 100 parts of p-phthalic acids-hexamethylene diamine complex salt and 70 parts of M-phthalic acid-hexamethylene diamines
Complex salt is made into the nylon saline solution of mass fraction 60% for raw material, concentrates nylon saline solution under the conditions of 170 DEG C, obtain 78%～
82% binary acid and diamine concentrated solution, meanwhile add 8.5 parts of nano barium sulfates, 5 parts of end-capping reagent benzoic acid and 2 parts
Catalyst sodium hypophosphite carry out prepolymerization, control prepolymerization temperature at 210 DEG C～230 DEG C, discharge the hydrone in concentrated solution,
Prepolymerization time controlled at 2 hours；Pressure is 1.8～2.0MPa；After the completion of prepolymerization, pressure unloads to normal pressure, prepolymer
It is expelled directly out from bottom valve, cooling, be ground into prepolyer granule (granule of 0.5～2mm size)；Prepolyer granule is through at 100 DEG C
Lower vacuum drying 12 hours, then progressively heats up and carries out solid phase polycondensation, and condensation temperature during polycondensation controls 240 DEG C, and vacuum is
20Pa, polycondensation time control is 14 hours, obtains semi-aromatic nylon resin；
(2) prepare semi-aromatic nylon composite：Semi-aromatic nylon resin 100 mass parts that be obtained step (1) and 30 matter
Amount part percent grafting is 0.71% glycidyl methacrylate graft ethylene-octene copolymer mix homogeneously, adds double in the same direction spiral shells
Bar extruder hopper, 1～9 section of temperature control of screw rod be 288 DEG C, 288 DEG C, 293 DEG C, 293 DEG C, 298 DEG C, 308 DEG C, 318 DEG C,
308 DEG C, 298 DEG C, rotating speed is 200r/min, carries out extrusion molding, prepared semi-aromatic nylon composite by screw extruder.
Comparative example 4：
A kind of semi-aromatic nylon composite, it is mainly formed by the component mixed preparing of following mass fraction：
100 parts of semi-aromatic nylon resin；
30 parts of glycidyl methacrylate graft ethylene-octene copolymer (toughener)；
8.5 parts of nano barium sulfate and
The percent grafting of wherein glycidyl methacrylate graft ethylene-octene copolymer is 0.71% (0.001x in this example).
In above-mentioned semi-aromatic nylon composite, semi-aromatic nylon resin is mainly by the aggregated reaction of raw material of following mass fraction
After prepare：
P-phthalic acid -100 parts of hexamethylene diamine complex salt,
M-phthalic acid -70 parts of hexamethylene diamine complex salt,
5 parts of benzoic acid, and
0.2 part of sodium hypophosphite.
The preparation method of the semi-aromatic nylon composite of above-mentioned comparative example, specifically includes following steps：
(1) synthesize semi-aromatic nylon resin：
Under the conditions of water does reaction medium, joined with 100 parts of p-phthalic acid hexamethylene diamines and 70 parts of M-phthalic acid hexamethylene diamines for raw material
Become the nylon saline solution of mass fraction 60%, concentrate nylon saline solution under the conditions of 170 DEG C, obtain 78%～82% nylon salt
Concentrated solution, meanwhile adds 5 parts of end-capping reagent benzoic acid and 2 parts of catalyst sodium hypophosphite to carry out prepolymerization, controls pre-
Polymerization temperature, at 210 DEG C～230 DEG C, discharges the hydrone in concentrated solution, and prepolymerization time controlled at 2 hours；Pressure be 1.8～
2.0MPa；After the completion of prepolymerization, pressure unloads to normal pressure, and prepolymer is expelled directly out from bottom valve, cooling, is ground into prepolymer
Grain (granule of 0.5～2mm size)；Prepolyer granule through at 100 DEG C be vacuum dried 12 hours, then progressively heat up into
Row vacuum solidification solid phase polycondensation, solidification temperature during vacuum solidification polycondensation controls 240 DEG C, and vacuum is 20Pa, solidification polymerization
Polycondensation time control is 14 hours, obtains semi-aromatic nylon resin；
(2) prepare semi-aromatic nylon composite：Semi-aromatic nylon resin 100 mass parts that be obtained step (1) and 30 matter
Amount part percent grafting is 0.71% glycidyl methacrylate graft ethylene-octene copolymer, 8.5 mass parts nano barium sulfates
(200nm<D50<600nm) mix homogeneously, adds parallel dual-screw extruding machine hopper, and 1～9 section of temperature control of screw rod is
288 DEG C, 288 DEG C, 293 DEG C, 293 DEG C, 298 DEG C, 308 DEG C, 318 DEG C, 308 DEG C, 298 DEG C, rotating speed is 200r/min, leads to
Cross screw extruder and carry out extrusion molding, prepared semi-aromatic nylon composite.
From embodiment 4 with comparative example 4 as can be seen that the nano barium sulfate using equivalent is modified through row to semi-aromatic nylon, in situ
Two kinds of addition manners of polymer and blending are all effectively controlled the warpage size of material, but blending adds nano barium sulfate to material
Reinforced effects not as good as polymerization in add, meanwhile, the notch sensitivity of material substantially increases (referring to table 1 below).
Embodiment 5：
A kind of semi-aromatic nylon composite of present invention, it is mainly formed by the component mixed preparing of following mass fraction：
100 parts of semi-aromatic nylon resin；
8 parts of glycidyl methacrylate graft ethylene-octene copolymer (toughener)；With
The percent grafting of wherein glycidyl methacrylate graft ethylene-octene copolymer is that 1.44% (the present embodiment is equivalent to
0.003x).
In above-mentioned semi-aromatic nylon composite, semi-aromatic nylon resin is mainly by the aggregated reaction of raw material of following mass fraction
After prepare：
100 parts of p-phthalic acid-ten two carbon diamidogen complex salt,
75 parts of caprolactam,
Nano barium sulfate (200nm<D50<600nm) 17.5 parts,
3.5 parts of benzoic acid, and
0.2 part of sodium hypophosphite.
The preparation method of the semi-aromatic nylon composite of above-mentioned the present embodiment, specifically includes following steps：
(1) synthesize semi-aromatic nylon resin：
Under the conditions of water does reaction medium, it is former with 100 parts of p-phthalic acid-ten two carbon diamidogen complex salt and 75 parts of caprolactams
Material is made into the nylon saline solution of mass fraction 60%, concentrates nylon saline solution, obtain the two of 78%～82% under the conditions of 170 DEG C
Unit's acid and diamine concentrated solution, meanwhile add urging of 17.5 parts of nano barium sulfates, 3.5 parts of end-capping reagent benzoic acid and 2 parts
Agent sodium hypophosphite carries out prepolymerization, controls prepolymerization temperature at 210 DEG C～230 DEG C, discharges the hydrone in concentrated solution, in advance
Polymerization time controlled at 2 hours；Pressure is 1.8～2.0MPa；After the completion of prepolymerization, pressure unloads to normal pressure, prepolymer from
Bottom valve is expelled directly out, cooling, is ground into prepolyer granule (granule of 0.5～2mm size)；Prepolyer granule is through at 100 DEG C
Lower vacuum drying 12 hours, then progressively heats up and carries out solid phase polycondensation, and condensation temperature during polycondensation controls 240 DEG C, and vacuum is
20Pa, polycondensation time control is 14 hours, obtains semi-aromatic nylon resin；
(2) prepare semi-aromatic nylon composite：Semi-aromatic nylon resin 100 mass parts that be obtained step (1) and 8 matter
Amount part percent grafting is 1.44% glycidyl methacrylate graft ethylene-octene copolymer mix homogeneously, adds double in the same direction spiral shells
Bar extruder hopper, 1～9 section of temperature control of screw rod be 273 DEG C, 273 DEG C, 278 DEG C, 278 DEG C, 283 DEG C, 293 DEG C, 303 DEG C,
293 DEG C, 283 DEG C, rotating speed is 200r/min, carries out extrusion molding, prepared semi-aromatic nylon composite by screw extruder.
Comparative example 5：
A kind of semi-aromatic nylon composite, it is mainly formed by the component mixed preparing of following mass fraction：
100 parts of semi-aromatic nylon resin；
8 parts of glycidyl methacrylate graft ethylene-octene copolymer (toughener)；
35 parts of nano barium sulfate and
The percent grafting of wherein glycidyl methacrylate graft ethylene-octene copolymer is 1.44% (0.003x in this example).
In above-mentioned semi-aromatic nylon composite, semi-aromatic nylon resin is mainly by the aggregated reaction of raw material of following mass fraction
After prepare：
100 parts of p-phthalic acid-ten two carbon diamidogen complex salt,
75 parts of caprolactam,
3.5 parts of benzoic acid, and
0.2 part of sodium hypophosphite.
The preparation method of the semi-aromatic nylon composite of above-mentioned comparative example, specifically includes following steps：
(1) synthesize semi-aromatic nylon resin：
Under the conditions of water does reaction medium, it is former with 100 parts of p-phthalic acid-ten two carbon diamidogen complex salt and 75 parts of caprolactams
Material is made into the nylon saline solution of mass fraction 60%, concentrates nylon saline solution, obtain 78%～82% Buddhist nun under the conditions of 170 DEG C
Imperial salt concentrated solution, meanwhile adds 3.5 parts of end-capping reagent benzoic acid and 2 parts of catalyst sodium hypophosphite to carry out prepolymerization,
Control prepolymerization temperature at 210 DEG C～230 DEG C, discharge the hydrone in concentrated solution, prepolymerization time controlled at 2 hours；Pressure
For 1.8～2.0MPa；After the completion of prepolymerization, pressure unloads to normal pressure, and prepolymer is expelled directly out from bottom valve, cooling, is ground into
Prepolyer granule (granule of 0.5～2mm size)；Prepolyer granule through at 100 DEG C be vacuum dried 12 hours, then by
Step intensification carries out vacuum solidification solid phase polycondensation, and solidification temperature during vacuum solidification polycondensation controls 240 DEG C, and vacuum is 20Pa,
Solidification polymerization polycondensation time control is 14 hours, obtains semi-aromatic nylon resin；
(2) prepare semi-aromatic nylon composite：Semi-aromatic nylon resin 100 mass parts that be obtained step (1) and 8 matter
Measure the glycidyl methacrylate graft ethylene-octene copolymer that part percent grafting is 1.44%, 35 parts of nano barium sulfates mixing all
Even, add parallel dual-screw extruding machine hopper, 1～9 section of temperature control of screw rod be 273 DEG C, 273 DEG C, 278 DEG C, 278 DEG C,
283 DEG C, 293 DEG C, 303 DEG C, 293 DEG C, 283 DEG C, rotating speed is 200r/min, carries out extrusion molding by screw extruder, system
Obtain semi-aromatic nylon composite.
Compared with comparative example 5, comparative example 5 with the addition of the nano-sulfur of twice embodiment 5 by way of blending to embodiment 5
Sour barium, substantial amounts of inorganic reinforcing filler is used in mixed way jointly with toughener, and the heavy damage performance of material, except warpage size
Other outer performance degradations (referring to table 1 below).
Embodiment 6：
A kind of semi-aromatic nylon composite of present invention, it is mainly formed by the component mixed preparing of following mass fraction：
100 parts of semi-aromatic nylon resin；
15 parts of glycidyl methacrylate graft ethylene-octene copolymer (toughener)；With
The percent grafting of wherein glycidyl methacrylate graft ethylene-octene copolymer is that 0.60% (the present embodiment is equivalent to
0.001x).
In above-mentioned semi-aromatic nylon composite, semi-aromatic nylon resin is mainly by the aggregated reaction of raw material of following mass fraction
After prepare：
P-phthalic acid -100 parts of decamethylene diamine complex salt,
M-phthalic acid -90 parts of decamethylene diamine complex salt,
(2 μm of glass microballoon<D50<5 μm) 19 parts
6 parts of benzoic acid, and
0.24 part of sodium hypophosphite.
The preparation method of the semi-aromatic nylon composite of above-mentioned the present embodiment, specifically includes following steps：
(1) synthesize semi-aromatic nylon resin：
Under the conditions of water does reaction medium, with 100 parts of p-phthalic acids-decamethylene diamine complex salt and 90 parts of M-phthalic acid-decamethylene diamines
Complex salt is made into the nylon saline solution of mass fraction 60% for raw material, concentrates nylon saline solution under the conditions of 170 DEG C, obtain 78%～
82% binary acid and diamine concentrated solution, meanwhile add 19 parts of glass microballoons, 6 parts of end-capping reagent benzoic acid and 2.4 parts
Catalyst sodium hypophosphite carry out prepolymerization, control prepolymerization temperature at 210 DEG C～230 DEG C, discharge the hydrone in concentrated solution,
Prepolymerization time controlled at 2 hours；Pressure is 1.8～2.0MPa；After the completion of prepolymerization, pressure unloads to normal pressure, prepolymer
It is expelled directly out from bottom valve, cooling, be ground into prepolyer granule (granule of 0.5～2mm size)；Prepolyer granule is through at 100 DEG C
Lower vacuum drying 12 hours, then progressively heats up and carries out solid phase polycondensation, and condensation temperature during polycondensation controls 240 DEG C, and vacuum is
20Pa, polycondensation time control is 14 hours, obtains semi-aromatic nylon resin；
(2) prepare semi-aromatic nylon composite：Semi-aromatic nylon resin 100 mass parts that be obtained step (1) and 15 matter
Amount part percent grafting is 0.60% glycidyl methacrylate graft ethylene-octene copolymer mix homogeneously, adds double in the same direction spiral shells
Bar extruder hopper, 1～9 section of temperature control of screw rod be 281 DEG C, 281 DEG C, 286 DEG C, 286 DEG C, 291 DEG C, 301 DEG C, 311 DEG C,
301 DEG C, 291 DEG C, rotating speed is 200r/min, carries out extrusion molding, prepared semi-aromatic nylon composite by screw extruder.
Comparative example 6：
A kind of semi-aromatic nylon composite of present invention, it is mainly formed by the component mixed preparing of following mass fraction：
100 parts of semi-aromatic nylon resin；
15 parts of glycidyl methacrylate graft ethylene-octene copolymer (toughener)；With
The percent grafting of wherein glycidyl methacrylate graft ethylene-octene copolymer is 0.60% (0.001x in this example).
In above-mentioned semi-aromatic nylon composite, semi-aromatic nylon resin is mainly by the aggregated reaction of raw material of following mass fraction
After prepare：
P-phthalic acid -100 parts of decamethylene diamine complex salt,
M-phthalic acid -90 parts of decamethylene diamine complex salt,
(2 μm of glass microballoon<D50<5 μm) 40 parts,
6 parts of benzoic acid, and
0.24 part of sodium hypophosphite.
The preparation method of the semi-aromatic nylon composite of above-mentioned the present embodiment, specifically includes following steps：
(1) synthesize semi-aromatic nylon resin：
Under the conditions of water does reaction medium, with 100 parts of p-phthalic acids-decamethylene diamine complex salt and 90 parts of M-phthalic acid-decamethylene diamines
Complex salt is made into the nylon saline solution of mass fraction 60% for raw material, concentrates nylon saline solution under the conditions of 170 DEG C, obtain 78%～
82% nylon salt concentrated solution, meanwhile adds the catalyst of 40 parts of glass microballoons, 6 parts of end-capping reagent benzoic acid and 2.4 parts
Sodium hypophosphite carries out prepolymerization, controls prepolymerization temperature at 210 DEG C～230 DEG C, discharges the hydrone in concentrated solution, prepolymerization
Time control was at 2 hours；Pressure is 1.8～2.0MPa；After the completion of prepolymerization, pressure unloads to normal pressure, cools down, and takes out and produces
Thing, is ground into prepolyer granule (granule of 0.5～2mm size)；Prepolyer granule is through being vacuum dried 12 at 100 DEG C
Hour, then progressively heat up and carry out vacuum solidification solid phase polycondensation, solidification temperature during vacuum solidification polycondensation controls 240 DEG C, vacuum
Spend for 20Pa, solidification polymerization polycondensation time control is 14 hours, obtains semi-aromatic nylon resin；
(2) prepare semi-aromatic nylon composite：Semi-aromatic nylon resin 100 mass parts that be obtained step (1) and 15 matter
Amount part percent grafting is 0.60% glycidyl methacrylate graft ethylene-octene copolymer mix homogeneously, adds double in the same direction spiral shells
Bar extruder hopper, 1～9 section of temperature control of screw rod be 281 DEG C, 281 DEG C, 286 DEG C, 286 DEG C, 291 DEG C, 301 DEG C, 311 DEG C,
301 DEG C, 291 DEG C, rotating speed is 200r/min, carries out extrusion molding, prepared semi-aromatic nylon composite by screw extruder.
Compared with comparative example 6, comparative example 6 adds substantial amounts of inorganic filler, performance boost in being polymerized in the original location to embodiment 6
Substantially, the stirring of polymerization later stage is difficult but in comparative example 6, and can not smoothly discharging, product can only knock out in kettle, in polymerization
There is restriction (referring to table 1 below) to addition in the method adding reinforcer.
Embodiment 7：
A kind of semi-aromatic nylon composite of present invention, it is mainly formed by the component mixed preparing of following mass fraction：
100 parts of semi-aromatic nylon resin；
20 parts of maleic anhydride grafted ethene-octene copolymer (toughener)；
The percent grafting of wherein maleic anhydride grafted ethene-octene copolymer is the 0.73% (amido link of 1000g resin in the present embodiment
Molal quantity x is 7.34,0.73% corresponding 0.001x).
In above-mentioned semi-aromatic nylon composite, semi-aromatic nylon resin is mainly by the aggregated reaction of raw material of following mass fraction
After prepare：
58.86 parts of p-phthalic acid,
45.69 parts of adipic acid,
77.45 part hexamethylene diamine,
Nanometer wollastonite (200nm<D50<800nm) 9 parts,
5.5 parts of benzoic acid, and
0.22 part of sodium hypophosphite.
The key property of product manufactured in the present embodiment is suitable with embodiment 1.
The performance test results of the semi-aromatic nylon composite that above-described embodiment and comparative example obtain are summarized as follows shown in table 1：
Table 1：Embodiment 1-6 and the properties of comparative example gained semi-aromatic nylon composite
In upper table 1, the method for testing of every mechanical performance index is as follows：
Tensile strength according to GB/T1040.2 standard testing semi-aromatic nylon composite material test piece；
Bending strength according to GB/T9341-2008 standard testing semi-aromatic nylon composite material test piece and bending moduluses；
Simple beam impact strength according to GB/T1043.1 standard testing semi-aromatic nylon composite material test piece.
In upper table 1, heat distortion temperature measures in the following manner：
According to GB/T1634.2-2004 standard, measure heat distortion temperature under 0.45MPa load.
Upper table 1 warp value measures in the following manner：
The injection sheet coupon of a size of 100mm × 100mm × 1mm is placed on platform, is 50mm with width, weight 2kg
Iron plate push down the side of sample, measure the height of sample warpage from opposite side with clearance gauge.
The various embodiments described above are determined by the following procedure with the percent grafting of toughener in comparative example：Grafting toughening agent is placed in Soxhlet
In extractor, with acetone extraction about 24h, to remove a small amount of free state MAH and oligomer MAH, extracting will be produced after terminating
Thing is placed in baking oven and dries.Accurately weigh 0.15g graft after purification, put in 100mL dimethylbenzene, add 2～3
Drip deionized water and the hydrolysis of 2～3 DMF promotion anhydride, backflow dissolving 1h, with the KOH- ethanol mark of 0.05mol/L
The titration of quasi- solution (preparing with reference to GB/T601-2002 method), makees indicator with phenolphthalein-ethanol solution, and does blank experiment.
It is calculated as follows percent grafting：
In above formula：
The percent grafting of the graft after G is refined, unit %；
V0The volume of the KOH- ethanol standard solution that blank experiment consumes, Unit/mL；
V1The volume of the KOH- ethanol standard solution that graft product consumes, Unit/mL；
C KOH- ethanol concentration of standard solution, unit mol/L；
The quality of W purification graft, unit g；
The molecular weight of M grafting material (maleic anhydride, glycidyl methacrylate).
Claims (10)
1. a kind of semi-aromatic nylon composite is it is characterised in that described semi-aromatic nylon composite is mainly by following mass parts
The component mixed preparing of number forms：
100 parts of semi-aromatic nylon；
2～50 parts of toughener；
Described semi-aromatic nylon is mainly prepared by after the aggregated reaction of raw material of following mass fraction：
The mixing of binary acid A and diamine A, or 100 parts of nylon complex salt A；
The mixing of binary acid B and diamine B, or 70～250 parts of nylon complex salt B；
8～35 parts of high fineness reinforcer,
1.5～22 parts of end-capping reagent, and
0.2～0.4 part of catalyst；
Described toughener is the olefinic copolymer after graft modification, and the percent grafting of toughener is 0.0005x～0.003x matter
Amount fraction；Wherein；X is the value of calculation of the amido link mole contained by semi-aromatic nylon described in 1000g.
2. semi-aromatic nylon composite according to claim 1 is it is characterised in that described binary acid A is terephthaldehyde
Acid, described diamine A is one of hexamethylene diamine, nonamethylene diamine, decamethylene diamine, 12 carbon diamines, 13 carbon diamines；Institute
State the reaction product that nylon complex salt A is binary acid A and diamine A.
3. semi-aromatic nylon composite according to claim 2 is it is characterised in that described binary acid B is isophthalic diformazan
Acid, adipic acid, decanedioic acid or SL-AH, described diamine B is hexamethylene diamine, nonamethylene diamine, decamethylene diamine, 12 carbon two
One of first amine, 13 carbon diamines；Described nylon complex salt B be binary acid B and diamine B reaction product or
For caprolactam or lauric lactam.
4. semi-aromatic nylon composite according to claim 1 is it is characterised in that described high fineness reinforcer is
One of nano barium sulfate, nanomete talc powder, nanometer wollastonite, nano mica powder, glass microballoon.
5. semi-aromatic nylon composite according to claim 1 is it is characterised in that described end-capping reagent is benzoic acid, 2-
One of naphthoic acid, 2- naphthalene acetic acid.
6. semi-aromatic nylon composite according to claim 1 it is characterised in that described catalyst be ortho phosphorous acid potassium,
One of sodium hypophosphite, ortho phosphorous acid magnesium, Lime Hypophosphate, ortho phosphorous acid zinc.
7. the semi-aromatic nylon composite according to any one of claim 1～6 is it is characterised in that described is toughness reinforcing
Agent is maleic anhydride grafted ethene-octene copolymer, maleic anhydride is grafted EP rubbers, glycidyl methacrylate graft second
Alkene-octene copolymer or styrene butadiene styrene block copolymer (SBS).
8. a kind of preparation method of semi-aromatic nylon composite as any one of claim 2～7, comprises the following steps：
(1) synthesize semi-aromatic nylon resin：Under the conditions of water does reaction medium, with described binary acid A and diamine A and two
Unit acid B and diamine B is made into binary acid and diamine concentrated solution for raw material, or is combined with nylon with described nylon complex salt A
Salt B is made into nylon saline solution for raw material, is subsequently adding high fineness reinforcer, end-capping reagent and catalyst and carries out prepolymerization, controls
Prepolymerization temperature, at 180 DEG C～240 DEG C, discharges the hydrone in concentrated solution, and prepolymerization time controlled at 0.1～5 hour；Pressure
For 0.8～2.5MPa；After the completion of prepolymerization, pressure unloads to normal pressure, and prepolymer is expelled directly out from bottom valve, cooling, is ground into
Prepolyer granule；Prepolyer granule, after drying, carries out solid phase polycondensation under the heating condition that progressively heats up, and obtains semiaromatic Buddhist nun
Imperial resin；
(2) prepare semi-aromatic nylon composite：The semi-aromatic nylon resin that be obtained step (1) and the increasing of certain percent grafting
Tough dose, functional aid is mixed in proportion, then carries out extrusion molding, prepared semi-aromatic nylon composite by screw extruder.
9. preparation method according to claim 8 it is characterised in that：Described binary acid and the concentration control of diamine concentrated solution
Make 70%～90%；Prepolymerization temperature control is at 210 DEG C～230 DEG C；Prepolymerization time controlled at 0.5～2 hour；
Condensation temperature during described solid phase polycondensation is controlled to 170 DEG C～260 DEG C, and vacuum is 1～1000Pa, polycondensation time control
For 5～25 hours.
10. preparation method according to claim 8 or claim 9 it is characterised in that：Described screw extruder is double in the same direction spiral shells
Bar extruder, 1～9 section of temperature of screw rod of this screw extruder is controlled to successively：(y-10)℃、(y-10)℃、(y-5)℃、(y-5)℃、
(y) DEG C, (y+10) DEG C, (y+20) DEG C, (y+10) DEG C, (y) DEG C, y is the fusing point of semi-aromatic nylon resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510486596.5A CN106433113B (en) | 2015-08-11 | 2015-08-11 | Semi-aromatic nylon composite material and preparation method |
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| CN108003341A (en) * | 2017-12-29 | 2018-05-08 | 东莞市意普万尼龙科技股份有限公司 | High temperature resistant low water absorption rate copolymer nylon and preparation method thereof |
| CN111087610A (en) * | 2019-12-25 | 2020-05-01 | 重庆晟淦新材料科技有限公司 | Industrial synthesis method of semi-aromatic high-temperature-resistant PA12T |
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