CN106147221A - Fiberglass reinforced fire retardant heat conduction semiaromatic copolymer nylon composite and preparation method thereof - Google Patents
Fiberglass reinforced fire retardant heat conduction semiaromatic copolymer nylon composite and preparation method thereof Download PDFInfo
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- CN106147221A CN106147221A CN201510208565.3A CN201510208565A CN106147221A CN 106147221 A CN106147221 A CN 106147221A CN 201510208565 A CN201510208565 A CN 201510208565A CN 106147221 A CN106147221 A CN 106147221A
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Abstract
A kind of fiberglass reinforced fire retardant heat conduction semiaromatic copolymer nylon composite of the present invention, its by following mass fraction component process be prepared from: semiaromatic copolymer polyamide resin 25%～50%；Glass fibre 25%～55%；Heat filling 10%～25% and fire retardant 6%～20%.The preparation method of this semiaromatic copolymer nylon composite includes: be first vacuum dried 8～12 hours at 100 DEG C by semiaromatic copolymer polyamide resin, then semiaromatic copolymer polyamide resin, fire retardant, heat filling, Masterbatch are stirred in high speed agitator compounding, it is eventually adding in double screw extruder hopper, glass fibre is added from double screw extruder side simultaneously, the temperature of double screw extruder controls at 250 DEG C～330 DEG C, it is thus achieved that fiberglass reinforced fire retardant heat conduction semiaromatic copolymer nylon composite.The product of the present invention have high fluidity, high intensity, low warpage, can be fire-retardant, without floating fine phenomenon and have the advantages such as heat conduction function.
Description
Technical field
The invention belongs to high temperature resistant, high intensity, high stability nylon and preparing technical field thereof, particularly relate to a kind of semiaromatic altogether
Poly-nylon composite materials and preparation method thereof.
Background technology
Semi-aromatic nylon is to be obtained with aliphatic diamine or diacid polycondensation by aromatic rings diacid or diamidogen, draws in nylon molecules main chain
Enter aromatic rings, improve thermostability and the mechanical performance of material, reduce water absorption rate, improve dimensional stability, filled up logical
By the blank between engineering plastics (such as amorphous nylon, polyester) and very-high performance material (such as PEEK, polysulfones and LCP).
In recent years, electronic and electrical equipment develops towards miniaturization, integrated densification, high performance direction, and its shell is more and more lighter
Quantify, thin-walled property, it is desirable to material therefor have high fluidity, high intensity, low warpage, heat conduction function and can be fire-retardant feature,
And casing products surface is without precipitation phenomenon.PA6, PA66 material water absorption rate of tradition is high, causes serious warpage, it is impossible to meet
Requirement, PPS poor processability, LCP is expensive.Semi-aromatic nylon has excellent cost performance, is first-selected ideal material.
But, existing semi-aromatic nylon resin is in the characteristics such as anti-flammability, heat conduction function, mechanical property, warpage preventing and outward appearance
Also needing to improve further, its combination property need further bar.
US4603166、US4603193、US4831108、US4163101、US5387645、US5112685、US5153250、
The american documentation literatures such as US5500473, US5981692, US5516882 and CN1537881A, CN1127266A,
The Chinese patent literatures such as CN1246490A, CN1227232A disclose the synthetic method of semi-aromatic nylon resin, but to semiaromatic
Research shorter mention in terms of nylon resin modification.CN102076752A, CN101796138A have related to semi-aromatic nylon tree
The enhancing of fat is flame-retardant modified, but purpose is to reduce the corrosion effect to equipment, does not additionally account for semi-aromatic nylon matrix resin
The heat conduction function of alternative condition and composite.
Summary of the invention
The technical problem to be solved is, overcomes the deficiency and defect mentioned in background above technology, it is provided that one has
High fluidity, high intensity, low warpage, almost without floating fine phenomenon and can have heat conduction in fire-retardant and preparation product casing surface
The fiberglass reinforced semiaromatic copolymer nylon composite of function, correspondingly provides the preparation side of this semiaromatic copolymer nylon composite
Method.
For solving above-mentioned technical problem, the technical scheme that the present invention proposes is a kind of fiberglass reinforced fire retardant heat conduction semiaromatic copolymer nylon
Composite, its mainly by following mass fraction component process be prepared from:
Semiaromatic copolymer polyamide resin 25%～50%；
Glass fibre 25%～55%；
Heat filling 10%～25%；With
Fire retardant 6%～20%
Above-mentioned fiberglass reinforced fire retardant heat conduction semiaromatic copolymer nylon composite, it is preferred that it is mainly by following mass fraction
Component processing is prepared from:
Semiaromatic copolymer polyamide resin 30%～40%；
Glass fibre 30%～45%；
Heat filling 12%～20%；With
Fire retardant 7%～15%
Above-mentioned fiberglass reinforced fire retardant heat conduction semiaromatic copolymer nylon composite, it is furthermore preferred that it is mainly by following mass fraction
Component processing be prepared from:
Semiaromatic copolymer polyamide resin 32%～38%；
Glass fibre 35%～42%；
Heat filling 14%～18%；With
Fire retardant 8%～12%.
Above-mentioned fiberglass reinforced fire retardant heat conduction semiaromatic copolymer nylon composite, it is furthermore preferred that described semiaromatic copolymer nylon tree
The synthesis material of fat is aromatic acid, aliphatic dibasic acid, aliphatic diamine, lactams, amino carboxylic acid or lubricant.
In above-mentioned fiberglass reinforced fire retardant heat conduction semiaromatic copolymer nylon composite, it is furthermore preferred that described aromatic acid is
P-phthalic acid, M-phthalic acid, 2-methylterephthalic acid, 2,5-dichloroterephthalicacid acid, 2,6-naphthalene diacid, 2,7-naphthalene diacid,
One or several in 1,4-naphthalene diacid, 4,4 '-biphenyl dicarboxylic acid, diphenyl methane-4,4 '-dicarboxylic acids, sulfobenzide .-4,4 '-dicarboxylic acids
Kind；Particularly preferably p-phthalic acid and/or M-phthalic acid.
In above-mentioned fiberglass reinforced fire retardant heat conduction semiaromatic copolymer nylon composite, it is furthermore preferred that described aliphatic dibasic acid is
Malonic acid, succinic acid, 1,3-propanedicarboxylic acid, adipic acid, 1,5-pentanedicarboxylic acid., suberic acid, Azelaic Acid, decanedioic acid, dimethyl malonic acid, 3,3-
In diethyl succinic acid, 2-methyl adipic acid, 2,2-dimethylated pentanedioic acid, 1,3-cyclopentane dicarboxylic acid and 1,4-cyclohexane dicarboxylic acid
One or more；Particularly preferably adipic acid.
In above-mentioned fiberglass reinforced fire retardant heat conduction semiaromatic copolymer nylon composite, it is furthermore preferred that described aliphatic diamine is
1,4-butanediamine, 1,6-hexamethylene diamine, 1,7-heptamethylene diamine, 1,8-octamethylenediamine, 1,9-nonamethylene diamine, 1,10-decamethylene diamine, 1,11-hendecane two
Amine, 1,12-dodecamethylene diamine, 1,13-tridecane diamine, 2-methyl isophthalic acid, 5-pentanediamine, 2,2,4-trimethyl-1,6-hexamethylene diamine and 2-first
One or more in base-1,8-octamethylenediamine.Particularly preferably 1,6-hexamethylene diamine, 1,10-decamethylene diamine, 1,12-dodecamethylene diamine, 1,13-
One or more in tridecane diamine.The most micro-1,6-hexamethylene diamine.
In above-mentioned fiberglass reinforced fire retardant heat conduction semiaromatic copolymer nylon composite, it is furthermore preferred that described lactams is acyl in oneself
Amine and/or lauric lactam.
In above-mentioned fiberglass reinforced fire retardant heat conduction semiaromatic copolymer nylon composite, it is furthermore preferred that described amino carboxylic acid is ω-ammonia
At least one in base caproic acid, omega-amino n-nonanoic acid, omega-amino undecanoic acid, omega-amino lauric acid/dodecanoic acid.
In above-mentioned fiberglass reinforced fire retardant heat conduction semiaromatic copolymer nylon composite, it is furthermore preferred that described lubricant is erucic acid acyl
Amine, oleamide, ethylene bis-fatty acid amides, silicone (silicone content 70%～80%), lignite acid derivative (Bu Lv
The graceful P12 of lattice) at least one；It has lubrication, can improve mobility, reduces friction, improves de-in injection mo(u)lding
Mould, improves product surface, has high gloss, accelerates extrusion and injection molding process.Synthesis high fluidity semiaromatic copolymerization
During nylon, the addition of lubricant controls at 0.05wt%～1wt%, more preferably 0.1wt%～0.6wt%, most preferably 0.2wt%～
0.4wt%, our research indicate that lubricant addition is few, and mobility improves inconspicuous, and addition is high, causes resin mechanical property
Can decline.
Above-mentioned fiberglass reinforced fire retardant heat conduction semiaromatic copolymer nylon composite, it is preferred that described semiaromatic copolymer polyamide resin
Fusing point control at 250 DEG C～290 DEG C, more preferably 260 DEG C～280 DEG C, most preferably 270 DEG C～275 DEG C.Our research table
Bright, fusing point is too low, and in strand, phenyl ring content reduces, and dimension stability reduces, and warpage increases；Fusing point is too high, phenyl ring
Content increases, and strand rigidity increases, and mobility declines, poor processability；Described semiaromatic copolymer polyamide resin relative
Viscosity is preferably controlled in 1.8～2.4, more preferably 1.9～2.3, most preferably 2.0～2.2.Our research indicate that, relative viscosity mistake
Low, the mechanical properties decrease of material；Relative viscosity is too high, and material flowability declines.
Above-mentioned fiberglass reinforced fire retardant heat conduction semiaromatic copolymer nylon composite, it is preferred that described semiaromatic copolymer polyamide resin
Fusing point, relative viscosity and lubricant meet above-mentioned condition and range the most simultaneously.
Above-mentioned fiberglass reinforced fire retardant heat conduction semiaromatic copolymer nylon composite, it is preferred that described glass fibre is flat glass
Fiber, its cross section is pancake and unconventional circle, can be specifically oval, half elliptic or other noncircular cross sections.
The main cross section axle in described cross section is 1.5～6 with the dimensional ratios of time cross section axis, more preferably 2.5～4.5, most preferably 3.0～4.0；
The chopped length of described glass fibre is 2～6mm, more preferably 3.0～4.5mm；The monofilament thickness of described glass fibre be 7～
10 μm, more preferably 8～9 μm.This preferred flat glass fiber surface uses silanes wetting agent to process, and is particularly well-suited to increase
The extruding and pelletizing process of strong thermoplastics PA, composite fluidity prepared is good, warpage is little for it, is particularly suitable for making
Thin-wall product.
Above-mentioned fiberglass reinforced fire retardant heat conduction semiaromatic copolymer nylon composite, it is preferred that described fire retardant is hypophosphites,
Preferably Methylethyl hypo-aluminum orthophosphate, diethyl hypo-aluminum orthophosphate, more preferably diethyl hypo-aluminum orthophosphate.The initial decomposition temperature of fire retardant
More than 300 DEG C, more preferably greater than 320 DEG C, most preferably greater than 330 DEG C, it can have good with described semiaromatic copolymer polyamide resin
Good is compound.In order to preferably strengthen the flame retardant effect of semiaromatic copolymer nylon composite, it is further preferred that described fire-retardant
Possibly together with Firebrake ZB in agent, its addition is the 1%～5% of the weight of fire retardant, more preferably 1.5%～4%, most preferably 2%～
3%.
Above-mentioned fiberglass reinforced fire retardant heat conduction semiaromatic copolymer nylon composite, it is preferred that described heat filling be micron order or
At least one in alumina in Nano level, magnesium oxide, zinc oxide, aluminium nitride, galapectite, boron nitride, carborundum.
The technical scheme of the invention described above is based primarily upon following thinking: when resins synthesis, addition lubricant is to improve mobility, and
Add heat filling when preparation strengthens flame-proof composite material, on the one hand improve the heat conductivity of material, on the other hand reduce product
Warpage；Thus provide one have high fluidity, high intensity, low warpage, can be fire-retardant, the product casing surface of preparation is almost
Without floating fine phenomenon and there is the semiaromatic copolymer nylon composite of heat conduction function.
As total technology design, it is multiple that the present invention also provides for a kind of above-mentioned fiberglass reinforced fire retardant heat conduction semiaromatic copolymer nylon
The preparation method of condensation material, comprises the following steps: described semiaromatic copolymer polyamide resin is vacuum dried at 100 DEG C 8～12
Hour, then semiaromatic copolymer polyamide resin, heat filling, fire retardant, Masterbatch are stirred in high speed agitator compounding,
It is eventually adding in double screw extruder hopper, described glass fibre is added from double screw extruder side, twin-screw extrusion simultaneously
The temperature of machine controls at 250 DEG C～330 DEG C, it is thus achieved that semiaromatic copolymer nylon composite.
The synthetic method of above-mentioned semiaromatic copolymer polyamide resin comprises the following steps: by binary acid and the diamine of equimolar amounts, urge
Agent, lubricant, deionized water join in the high-temperature high-pressure reaction kettle of 10L, displace air in still with High Purity Nitrogen, successively
Three times, and retained nitrogen atmospheric pressure 0.15MPa；Open stirring, in 1～3 hour, rise high-temperature to 200 DEG C～225 DEG C,
Now reactor pressure is 0.7MPa～2.5MPa, maintains this pressure 0.5～6 hours；Open vent valve and slowly exit, still
Interior temperature rises to 280 DEG C～310 DEG C, keeps 0～1 hour, discharging, obtains semiaromatic copolymer polyamide resin.
Compared with prior art, it is an advantage of the current invention that: semiaromatic copolymer nylon composite prepared by the present invention has well
Cost performance, this semiaromatic copolymer nylon composite have high fluidity, high intensity, low warpage, heat conduction, can be fire-retardant etc. spy
Point, easy machine-shaping, excellent combination property, the product casing surface of preparation is without floating fine phenomenon, and energy Quick diffusing device inside
Heat, improves service life.
It addition, the preparation method of the semiaromatic copolymer nylon composite of the present invention, step is simple, easily operates, low cost,
Good product quality, can promotion and application widely.
Detailed description of the invention
For the ease of understanding the present invention, below in conjunction with preferred embodiment, the present invention is made more comprehensively, describes meticulously, but this
The protection domain of invention is not limited to embodiment in detail below.
Unless otherwise defined, the implication that all technical term used hereinafter is generally understood that with those skilled in the art is identical.
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 semiaromatic copolymer nylon composite of the present invention, its mainly by following mass fraction component process be prepared from:
Semiaromatic copolymer polyamide resin 33.75 parts；
Glass fibre 40 parts；
Heat filling 15 parts
Masterbatch 1 part；
Composite flame-retardant agent 10.25 parts.
Synthon: p-phthalic acid (1554g), hexamethylene diamine (1090g), caprolactam (1360g), lubricant P12 (12g)
For the 0.3% of synthon quality, deionized water (1300g) joins in the high-temperature high-pressure reaction kettle of 10L, puts with High Purity Nitrogen
Swap out air in still, successively three times, and retained nitrogen atmospheric pressure 0.15MPa；Open stirring, in 1.5 hours, rise high-temperature
To 210 DEG C, now reactor pressure is 1.8MPa, maintains this pressure 4 hours；Open vent valve and slowly exit, temperature in still
Degree rises to 285～290 DEG C, keeps 20min, discharging, obtains semiaromatic copolymer nylon 6T/6.
The fusing point of this semiaromatic copolymer polyamide resin controls at 272 DEG C, and relative viscosity controls 2.1.Glass above-mentioned in the present embodiment
Glass fiber is flat glass fiber, and its cross section is pancake, and the main cross section axle in cross section is 3.5 with the dimensional ratios of time cross section axis,
The chopped length of glass fibre is 3.0mm；The monofilament thickness of glass fibre is 8～9 μm.Heat conduction above-mentioned in the present embodiment is filled out
Material is galapectite.Fire retardant above-mentioned in the present embodiment is diethyl hypo-aluminum orthophosphate (OP1230), the initial decomposition temperature of fire retardant
Degree is more than 300 DEG C.Fire retardant is also added with the Firebrake ZB of 0.25 part.
The preparation method of the fiberglass reinforced fire retardant heat conduction semiaromatic copolymer nylon composite that the present embodiment is above-mentioned, specifically includes following
Step: semiaromatic copolymer polyamide resin is vacuum dried at 100 DEG C 12 hours, then the semiaromatic of above-mentioned mass fraction is total to
Poly-nylon resin, fire retardant, heat filling and Masterbatch stir compounding in high speed agitator, are eventually adding double screw extruder
In hopper, the glass fibre of above-mentioned mass fraction is added from double screw extruder side, the temperature control of double screw extruder simultaneously
System at 260 DEG C～295 DEG C, concrete 1～9 district's temperature are followed successively by: 260 DEG C, 275 DEG C, 280 DEG C, 285 DEG C, 290 DEG C, 295 DEG C,
290 DEG C, 285 DEG C, 280 DEG C, head temperature is 285 DEG C；Mediate under conditions of rotating speed 250r/min, it is thus achieved that fiberglass reinforced hinders
Fire fire-retardant semiaromatic copolymer nylon composite.By to this composite products and carry out mechanical property, mobility, heat conductivity,
Anti-flammability, warpage, the test of outward appearance, acquired results is listed in the table below in 1.
Embodiment 2:
The proportioning of the semiaromatic copolymer nylon composite of the present embodiment is substantially the same manner as Example 1, the operating procedure of preparation and work
Skill Parameter Conditions is the most substantially the same manner as Example 1, and its difference is in the present embodiment that the semiaromatic copolymer polyamide resin selected is
PA6T/66, its fusing point is 271 DEG C, and relative viscosity is 2.12.The property indices of the present embodiment composite asks for an interview table 1 below.
In the present embodiment, semiaromatic copolymer polyamide resin is that the synthetic method of PA6T/66 comprises the following steps: by p-phthalic acid
(824g), 1,6-hexamethylene diamine (580g), nylon salt (2600g) and lubricant P12 (12g), deionized water (1300g)
Join in the high-temperature high-pressure reaction kettle of 10L, displace air in still, successively three times, and retained nitrogen atmospheric pressure with High Purity Nitrogen
0.15MPa；Opening stirring, in 1.5 hours, liter high-temperature is to 210 DEG C, and now reactor pressure is 1.8MPa, maintains
This pressure 1 hour；Opening vent valve and slowly exit, temperature in the kettle rises to 285 DEG C～290 DEG C, holding 20min, discharging,
Obtain semiaromatic copolymer polyamide resin PA6T/66.
Embodiment 3:
The proportioning of the semiaromatic copolymer nylon composite of the present embodiment is substantially the same manner as Example 1, the operating procedure of preparation and work
Skill Parameter Conditions is the most substantially the same manner as Example 1, and its difference is in the present embodiment that the semiaromatic copolymer polyamide resin selected is
PA6T/66/6, synthesis technique is with embodiment 1, and synthon is p-phthalic acid, hexamethylene diamine, nylon salt, caprolactam,
Lubricant P12 is the 0.3% of synthon, and its fusing point is 270 DEG C, and relative viscosity is 2.11.The present embodiment composite each
Item performance indications ask for an interview table 1 below.
Embodiment 4:
The proportioning of the semiaromatic copolymer nylon composite of the present embodiment is substantially the same manner as Example 1, the operating procedure of preparation and work
Skill Parameter Conditions is the most substantially the same manner as Example 1, and its difference is in the present embodiment that the semiaromatic copolymer polyamide resin selected is
PA6T/6I/6, synthesis technique is with embodiment 1, and synthon is p-phthalic acid, hexamethylene diamine, nylon salt, caprolactam,
Lubricant P12 is the 0.3% of synthon, and its fusing point is 273 DEG C, and relative viscosity is 2.13.The present embodiment composite each
Item performance indications ask for an interview table 1 below.
Embodiment 5:
The proportioning of the semiaromatic copolymer nylon composite of the present embodiment is substantially the same manner as Example 1, the operating procedure of preparation and work
Skill Parameter Conditions is the most substantially the same manner as Example 1, and its difference is in the present embodiment that the semiaromatic copolymer polyamide resin selected is
PA10T/6, synthesis technique is with embodiment 1, and synthon is p-phthalic acid, hexamethylene diamine, nylon salt, caprolactam,
Lubricant P12 is the 0.3% of synthon, and the property indices of the present embodiment composite asks for an interview table 1 below.
Table 1: the performance detection parameter of each embodiment product
Comparative example 6:
Main component and the proportioning of the semiaromatic copolymer nylon composite of the present embodiment are substantially the same manner as Example 1, and its difference exists
The semiaromatic copolymer polyamide resin selected in the present embodiment is PA6T/6, and its fusing point is 295 DEG C, and relative viscosity is 2.1；It addition,
Operating procedure and technological parameter condition prepared by the present embodiment product are the most substantially the same manner as Example 1, and it differs only in: double spiral shells
The temperature of bar extruder controls at 280 DEG C～315 DEG C, and concrete 1～9 district's temperature are followed successively by: 280 DEG C, 290 DEG C, 300 DEG C, 305 DEG C,
310 DEG C, 315 DEG C, 305 DEG C, 300 DEG C, 300 DEG C, head temperature is 305 DEG C.The properties of the present embodiment composite refers to
Mark asks for an interview table 2 below.
Comparative example 7:
Main component and the proportioning of the semiaromatic copolymer nylon composite of the present embodiment are substantially the same manner as Example 1, the behaviour of preparation
Making step and technological parameter condition is the most substantially the same manner as Example 1, it differs only in: the semiaromatic copolymerization that the present embodiment is selected
The relative viscosity of nylon resin PA6T/6 is 2.7, and the property indices of the present embodiment composite asks for an interview table 2 below.
Comparative example 8:
Main component and the proportioning of the semiaromatic copolymer nylon composite of the present embodiment are substantially the same manner as Example 1, the behaviour of preparation
Making step and technological parameter condition is the most substantially the same manner as Example 1, it differs only in: the glass fibre that the present embodiment is selected is
The glass fibre in typical circular cross section, the property indices of the present embodiment composite asks for an interview table 2 below.
Comparative example 9:
Main component and the proportioning of the semiaromatic copolymer nylon composite of the present embodiment are substantially the same manner as Example 1, the behaviour of preparation
Making step and technological parameter condition is the most substantially the same manner as Example 1, it differs only in: synthesize semiaromatic copolymerization in the present embodiment
Being not added with lubricant during nylon, the property indices of the present embodiment composite asks for an interview table 2 below.
Comparative example 10:
Semiaromatic copolymer polyamide resin 48.75 parts；
Glass fibre 40 parts；
Masterbatch 1 part；
Composite flame-retardant agent 10.25 parts
The semiaromatic copolymer polyamide resin of the present embodiment is prepared with embodiment 1, the semiaromatic copolymer nylon composite of the present embodiment
Operating procedure and technological parameter condition the most substantially the same manner as Example 1, its difference is: is not added with heat conduction in the present embodiment and fills out
Material, semi-aromatic nylon resin increases to 48.75 parts, and the property indices of the present embodiment composite asks for an interview table 2 below.
Table 2: the performance test results of each product in comparative example
Contrast through above-mentioned Tables 1 and 2 understands, and the fusing point of semiaromatic copolymer nylon is too high or relative viscosity is too high, composite wood
The mobility of material is deteriorated and has floating fine phenomenon；Selecting circular glass fiber, the composite warpage obtained substantially and has floating fibre；Poly-
Not adding lubricant during conjunction, the mobility of composite is deteriorated and has a small amount of floating fibre；Do not add Heat Conduction Material, the heat conduction system of composite
Number reduces.Optimal processing parameter is as follows: semiaromatic copolymer nylon prepared by the lubricant adding 0.3%, and control its fusing point at 270 DEG C～
275 DEG C, relative viscosity scope is at 2.0～2.2,40% flat glasses, 15% heat filling, 10% fire retardant.High stream can be prepared
Warpage dynamic, high-strength, low, heat conduction, the semiaromatic copolymer nylon composite of the characteristic such as fire-retardant.
In above example, method of testing and the standard of each performance parameter are as follows:
1. relative viscosity [η]
Being dissolved in concentrated sulphuric acid by the semiaromatic copolymer polyamide resin of test, obtaining concentration is 1g/dl, measures solution at 25 DEG C
Relative viscosity η r:
η r=t1/t0；
Wherein t0 represents the time (s) that solvent flows out, and t1 represents the time (s) that sample solution flows out, and η r is equal to solution with molten
The ratio of agent delivery time.
2. fusing point
Use the fusing point of prunus mume (sieb.) sieb.et zucc. Teller-torr benefit DSC1 Instrument measuring sample, under nitrogen atmosphere, be warming up to 10 DEG C/minute from room temperature
330 DEG C, keep 5min, room temperature when then cooling down with the speed of 10 DEG C/minute, then be warming up to 330 DEG C with the speed of 10 DEG C/minute,
Endotherm peak temperature now is melting point polymer.
3. mechanical property
The composite injection test bars of preparation, tests hot strength according to standard GB/T1040.2-2006, according to standard
GB/T9341-2008 test bending strength and bending modulus, test simple beam impact strength according to standard GB/T1043.1-2008.
4. mobility
Testing melt index according to standard GB/T3682-2000, test temperature is higher than melting point resin 30 DEG C, and loading load is
2.16kg。
5. electrical conductivity
According to standard ASTM D5470 testing conductive coefficient.
6. anti-flammability
Use batten test thick for 1.6mm according to standard UL94:2014, sample 23 DEG C, regulate 96 under 50% relative humidity
Test after hour.
7. warpage
The injection sheet coupon of a size of 100mm × 100mm × 1mm is placed on platform, is 50mm with width, weight
The iron plate of 2kg pushes down the side of sample, measures the height of sample warpage with clearance gauge from opposite side.
8. outward appearance
The sample of injection 5mm × 5mm × 1mm, by the floating fine situation of electron microscopic observation specimen surface.
Claims (10)
1. a fiberglass reinforced fire retardant heat conduction semiaromatic copolymer nylon composite, it is characterised in that it is mainly divided by following quality
The component processing of number is prepared from:
Fiberglass reinforced fire retardant heat conduction semiaromatic copolymer nylon composite the most according to claim 1, it is characterised in that its
Mainly processed by the component of following mass fraction and be prepared from:
Fiberglass reinforced fire retardant heat conduction semiaromatic copolymer nylon composite the most according to claim 2, it is characterised in that its
Mainly processed by the component of following mass fraction and be prepared from:
4. according to the fiberglass reinforced fire retardant heat conduction semiaromatic copolymer nylon composite according to any one of claims 1 to 3, its
Being characterised by, the synthon of described semiaromatic copolymer polyamide resin is aromatic acid, aliphatic dibasic acid, aliphatic two
Unit's amine, lactams, amino carboxylic acid or lubricant.
Fiberglass reinforced fire retardant heat conduction semiaromatic copolymer nylon composite the most according to claim 4, it is characterised in that:
Described aromatic acid be p-phthalic acid, M-phthalic acid, 2-methylterephthalic acid, 2,5-dichloroterephthalicacid acid,
2,6-naphthalene diacid, 2,7-naphthalene diacid, 1,4-naphthalene diacid, 4,4 '-biphenyl dicarboxylic acid, diphenyl methane-4,4 '-dicarboxylic acids, sulfobenzide.
-4,4 ' one or more in-dicarboxylic acids；
Described aliphatic dibasic acid is malonic acid, succinic acid, 1,3-propanedicarboxylic acid, adipic acid, 1,5-pentanedicarboxylic acid., suberic acid, Azelaic Acid, the last of the ten Heavenly stems
Diacid, dimethyl malonic acid, 3,3-diethyl succinic acid, 2-methyl adipic acid, 2,2-dimethylated pentanedioic acid, 1,3-Pentamethylene. dicarboxyl
One or more in acid and 1,4-cyclohexane dicarboxylic acid；
Described aliphatic diamine is 1,4-butanediamine, 1,6-hexamethylene diamine, 1,7-heptamethylene diamine, 1,8-octamethylenediamine, 1,9-nonamethylene diamine, 1,10-
Decamethylene diamine, 1,11-hendecane diamidogen, 1,12-dodecamethylene diamine, 1,13-tridecane diamine, 2-methyl isophthalic acid, 5-pentanediamine, 2,2,4-tri-
Methyl isophthalic acid, 6-hexamethylene diamine and 2-methyl isophthalic acid, one or more in 8-octamethylenediamine.
Described lactams is caprolactam and/or lauric lactam；
Described amino carboxylic acid is at least one in omega-amino caproic acid, omega-amino n-nonanoic acid, omega-amino undecanoic acid, omega-amino lauric acid/dodecanoic acid；
Described lubricant be in erucyl amide, oleamide, ethylene bis-fatty acid amides, silicone, lignite acid derivative extremely
Few one；The addition of lubricant controls at 0.05wt%～1wt%, more preferably 0.1wt%～0.6wt%, most preferably 0.2wt%～
0.4wt%.
6. according to the fiberglass reinforced fire retardant heat conduction semiaromatic copolymer nylon composite according to any one of claims 1 to 3, its
Being characterised by, the fusing point of described semiaromatic copolymer polyamide resin controls at 250 DEG C～290 DEG C, more preferably 260 DEG C～280 DEG C,
Preferably 270 DEG C～275 DEG C；Relative viscosity controls 1.8～2.4, more preferably 1.9～2.3, most preferably 2.0～2.2.
7. according to the fiberglass reinforced fire retardant heat conduction semiaromatic copolymer nylon composite according to any one of claims 1 to 3, its
Being characterised by, described glass fibre is flat glass fiber, and its cross section is pancake, the main cross section axle in described cross section and time horizontal stroke
The dimensional ratios of sectional axis is 1.5～6, more preferably 2.5～4.5, most preferably 3.0～4.0；The chopped length of described glass fibre is
2～6mm, more preferably 3.0～4.5mm；The monofilament thickness of described glass fibre is 7～10 μm, more preferably 8～9 μm.
8. according to the fiberglass reinforced fire retardant heat conduction semiaromatic copolymer nylon composite according to any one of claims 1 to 3, its
Being characterised by, described fire retardant is hypophosphites, preferably Methylethyl hypo-aluminum orthophosphate, diethyl hypo-aluminum orthophosphate, more preferably diethyl
Base hypo-aluminum orthophosphate；The initial decomposition temperature of fire retardant is more than 300 DEG C, more preferably greater than 320 DEG C, most preferably greater than 330 DEG C；
Described fiberglass reinforced fire retardant heat conduction semiaromatic copolymer nylon composite, it is characterised in that in described fire retardant possibly together with
Firebrake ZB, its addition is the 1%～5% of the weight of fire retardant, more preferably 1.5%～4%, most preferably 2%～3%.
9. according to the fiberglass reinforced fire retardant heat conduction semiaromatic copolymer nylon composite according to any one of claims 1 to 3, its
Being characterised by, described heat filling is micron order or alumina in Nano level, magnesium oxide, zinc oxide, aluminium nitride, galapectite, nitrogen
Change at least one in boron, carborundum.
10. the fiberglass reinforced fire retardant heat conduction semiaromatic copolymer nylon composite as according to any one of claim 1～9
Preparation method, comprises the following steps: described semiaromatic copolymer polyamide resin is vacuum dried at 100 DEG C 8～12 hours, so
After semiaromatic copolymer polyamide resin, fire retardant, heat filling, Masterbatch are stirred compounding in high speed agitator, be eventually adding
In double screw extruder hopper, described glass fibre is added from double screw extruder side, the temperature of double screw extruder simultaneously
Control at 250 DEG C～330 DEG C, it is thus achieved that fiberglass reinforced fire retardant heat conduction semiaromatic copolymer nylon composite.
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