CN106147221B - The thermally conductive semiaromatic copolymer nylon composite material and preparation method of fiberglass reinforced fire retardant - Google Patents
The thermally conductive semiaromatic copolymer nylon composite material and preparation method of fiberglass reinforced fire retardant Download PDFInfo
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Abstract
A kind of thermally conductive semiaromatic copolymer nylon composite material of fiberglass reinforced fire retardant of the invention is prepared: semiaromatic copolymer polyamide resin 25%~50% by the component processing of following mass fraction；Glass fibre 25%~55%；Heat filling 10%~25% and fire retardant 6%~20%.The preparation method of the semiaromatic copolymer nylon composite material includes: first to be dried in vacuo semiaromatic copolymer polyamide resin 8~12 hours at 100 DEG C, then semiaromatic copolymer polyamide resin, fire retardant, heat filling, Masterbatch are stirred to compounding in high speed agitator, 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 is controlled at 250 DEG C~330 DEG C, obtains the thermally conductive semiaromatic copolymer nylon composite material of fiberglass reinforced fire retardant.Product of the invention have many advantages, such as high fluidity, high intensity, low warpage, can it is fire-retardant, without floating fine phenomenon and there is thermally conductive function.
Description
Technical field
The invention belongs to high temperature resistant, high intensity, high stability nylon and its preparation technical field more particularly to a kind of half virtues
Fragrant copolymer nylon composite material and preparation method.
Background technique
Semi-aromatic nylon is to be obtained by aromatic rings diacid or diamines with aliphatic diamine or diacid polycondensation, in nylon molecules master
Aromatic rings is introduced in chain, is improved the heat resistance and mechanical performance of material, is reduced water absorption rate, improve dimensional stability, fill out
The sky between general engineering plastic (such as amorphous nylon, polyester) and very-high performance material (such as PEEK, polysulfones and LCP) is mended
It is white.
In recent years, electronic and electrical equipment develops towards miniaturization, integrated densification, high performance direction, and shell is more next
More lightweight, be thinning, it is desirable that material therefor have high fluidity, high intensity, low warpage, thermally conductive function and can be fire-retardant spy
Point, and casing products surface is without precipitation phenomenon.PA6, PA66 material water absorption rate of tradition are high, lead to serious warpage, Bu Nengman
Foot requires, PPS poor processability, and LCP is expensive.Semi-aromatic nylon has excellent cost performance, is preferred ideal material.
However, existing semi-aromatic nylon resin is in spies such as anti-flammability, thermally conductive function, mechanical property, warpage preventing and appearances
It also needs further to improve in property, comprehensive performance need further item.
US4603166、US4603193、US4831108、US4163101、US5387645、US5112685、
The american documentation literatures such as US5153250, US5500473, US5981692, US5516882 and CN1537881A,
The Chinese patent literatures such as CN1127266A, CN1246490A, CN1227232A disclose the synthetic method of semi-aromatic nylon resin,
But to the research shorter mention in terms of semi-aromatic nylon resin modified.CN102076752A, CN101796138A have been related to half
The enhancing of aramid fiber resin is flame-retardant modified, but purpose is the corrosion effect reduced to equipment, does not in addition account for semiaromatic Buddhist nun
The alternative condition of imperial matrix resin and the thermally conductive function of composite material.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the shortcomings of to mention in background above technology and defect, provide one
Kind have high fluidity, high intensity, low warpage, can fire-retardant and preparation product casing surface almost without floating fine phenomenon and have
The fiberglass reinforced semiaromatic copolymer nylon composite material of thermally conductive function, correspondingly provides the semiaromatic copolymer nylon composite material
Preparation method.
In order to solve the above technical problems, technical solution proposed by the present invention is total for a kind of thermally conductive semiaromatic of fiberglass reinforced fire retardant
Poly- nylon composite materials are mainly prepared by the component processing of following mass fraction:
Semiaromatic copolymer polyamide resin 25%~50%；
Glass fibre 25%~55%；
Heat filling 10%~25%；With
Fire retardant 6%~20%
The thermally conductive semiaromatic copolymer nylon composite material of above-mentioned fiberglass reinforced fire retardant, it is preferred that it is mainly by following quality
The component processing of score is prepared:
Semiaromatic copolymer polyamide resin 30%~40%；
Glass fibre 30%~45%；
Heat filling 12%~20%；With
Fire retardant 7%~15%
The thermally conductive semiaromatic copolymer nylon composite material of above-mentioned fiberglass reinforced fire retardant, it is furthermore preferred that it is mainly by following matter
The component processing of amount score is prepared:
Semiaromatic copolymer polyamide resin 32%~38%；
Glass fibre 35%~42%；
Heat filling 14%~18%；With
Fire retardant 8%~12%.
The thermally conductive semiaromatic copolymer nylon composite material of above-mentioned fiberglass reinforced fire retardant, it is furthermore preferred that the semiaromatic is copolymerized
The synthesis material of nylon resin be aromatic acid, aliphatic dibasic acid, aliphatic diamine, lactams, amino carboxylic acid or
Lubricant.
In the thermally conductive semiaromatic copolymer nylon composite material of above-mentioned fiberglass reinforced fire retardant, it is furthermore preferred that the aromatic series two
First acid is terephthalic acid (TPA), 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 acids, diphenyl methane -4,4 '-dicarboxylic acids, diphenyl sulfone -4,4 '-dicarboxyl
One or more of acid；Particularly preferably terephthalic acid (TPA) and/or M-phthalic acid.
In the thermally conductive semiaromatic copolymer nylon composite material of above-mentioned fiberglass reinforced fire retardant, it is furthermore preferred that the aliphatic two
First acid is malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, decanedioic acid, dimethyl malonic acid, 3,
3- diethyl succinic acid, 2- methyl adipic acid, 2,2- dimethylated pentanedioic acid, 1,3- cyclopentane dicarboxylic acid and 1,4- hexamethylene dicarboxyl
One or more of acid；Particularly preferably adipic acid.
In the thermally conductive semiaromatic copolymer nylon composite material of above-mentioned fiberglass reinforced fire retardant, it is furthermore preferred that the aliphatic two
First amine be 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 diamines, 1,12- dodecamethylene diamine, 1,13- tridecane diamine, 2- methyl-1,5- pentanediamine, 2,2,4- trimethyl-
1,6- hexamethylene diamine and 2- methyl-1, one or more of 8- octamethylenediamine.Particularly preferably 1,6- hexamethylene diamine, 1,10- decamethylene diamine,
One or more of 1,12- dodecamethylene diamine, 1,13- tridecane diamine.More preferable micro- 1,6- hexamethylene diamine.
In the thermally conductive semiaromatic copolymer nylon composite material of above-mentioned fiberglass reinforced fire retardant, it is furthermore preferred that the lactams is
Caprolactam and/or lauric lactam.
In the thermally conductive semiaromatic copolymer nylon composite material of above-mentioned fiberglass reinforced fire retardant, it is furthermore preferred that the amino carboxylic acid
For at least one of omega-amino caproic acid, omega-amino n-nonanoic acid, omega-amino undecanoic acid, omega-amino lauric acid/dodecanoic acid.
In the thermally conductive semiaromatic copolymer nylon composite material of above-mentioned fiberglass reinforced fire retardant, it is furthermore preferred that the lubricant is
Erucyl amide, oleamide, ethylene bis-fatty acid amides, silicone (silicone content 70%~80%), lignite acid derivative
At least one of (Brueggemann P12)；It can improve mobility with lubricating action, reduce friction, improve in injection molding
Release property improves product surface, has high gloss, accelerates extrusion and injection molding process.It is total to synthesize high fluidity semiaromatic
When poly- nylon, the additive amount of lubricant is controlled in 0.05wt%~1wt%, more preferable 0.1wt%~0.6wt%, most preferably
0.2wt%~0.4wt%, our research indicate that lubricant additive amount is few, mobility raising is unobvious, and additive amount is high, causes
Resin mechanical properties decrease.
The thermally conductive semiaromatic copolymer nylon composite material of above-mentioned fiberglass reinforced fire retardant, it is preferred that the semiaromatic is copolymerized Buddhist nun
The fusing point of imperial resin is controlled at 250 DEG C~290 DEG C, more preferable 260 DEG C~280 DEG C, most preferably 270 DEG C~275 DEG C.Ours grinds
Study carefully and show that fusing point is too low, phenyl ring content is reduced in strand, and dimension stability reduces, and warpage increases；Fusing point is excessively high, benzene
Ring content increases, and molecule chain rigidity increases, mobility decline, poor processability；The phase of the semiaromatic copolymer polyamide resin
1.8~2.4, more preferable 1.9~2.3, most preferably 2.0~2.2 are preferably controlled in viscosity.Our research indicate that relatively viscous
Spend low, the mechanical properties decrease of material；Relative viscosity is excessively high, material flowability decline.
The thermally conductive semiaromatic copolymer nylon composite material of above-mentioned fiberglass reinforced fire retardant, it is preferred that the semiaromatic is copolymerized Buddhist nun
Fusing point, relative viscosity and the lubricant of imperial resin particularly preferably meet above-mentioned condition range simultaneously.
The thermally conductive semiaromatic copolymer nylon composite material of above-mentioned fiberglass reinforced fire retardant, it is preferred that the glass fibre is flat
Flat glass fibre, section unconventional circle for pancake, specifically can be oval, half elliptic or other are non-circular
Section.The dimensional ratios of the main cross section axis in the section and time cross section axis are 1.5~6, more preferable 2.5~4.5, most preferably
3.0~4.0；The chopped length of the glass fibre is 2~6mm, more preferable 3.0~4.5mm；The monofilament of the glass fibre is thick
Degree is 7~10 μm, more preferable 8~9 μm.The preferred flat glass fiber surface is handled using silanes size, especially suitable
For enhancing the extruding and pelletizing process of thermoplastics PA, composite fluidity obtained is good, warpage is small, particularly suitable for
Make thin-wall product.
The thermally conductive semiaromatic copolymer nylon composite material of above-mentioned fiberglass reinforced fire retardant, it is preferred that the fire retardant is time phosphorus
Hydrochlorate, preferably Methylethyl hypo-aluminum orthophosphate, diethyl hypo-aluminum orthophosphate, more preferable diethyl hypo-aluminum orthophosphate.The starting of fire retardant point
It solves temperature and is greater than 300 DEG C, more preferably greater than 320 DEG C, most preferably greater than 330 DEG C can be with the semiaromatic copolymer nylon trees
Rouge has good compound.In order to preferably enhance the flame retardant effect of semiaromatic copolymer nylon composite material, it is further preferred that institute
It states and also contains zinc borate in fire retardant, additive amount is the 1%~5%, more preferable 1.5%~4% of the weight of fire retardant, optimal
Select 2%~3%.
The thermally conductive semiaromatic copolymer nylon composite material of above-mentioned fiberglass reinforced fire retardant, it is preferred that the heat filling is micro-
At least one of meter level or alumina in Nano level, magnesia, zinc oxide, aluminium nitride, galapectite, boron nitride, silicon carbide.
The technical solution of aforementioned present invention is based primarily upon following thinking: lubricant is added in resins synthesis to improve flowing
Property, and heat filling is added when preparation enhances flame retardant composite material, the thermal coefficient of material is on the one hand improved, is on the other hand dropped
The warpage of low product；To provide it is a kind of have high fluidity, high intensity, low warpage, can be fire-retardant, the product casing surface of preparation
Almost without floating fine phenomenon and with the semiaromatic copolymer nylon composite material of thermally conductive function.
As a general technical idea, the present invention also provides a kind of thermally conductive semiaromatic copolymerization of above-mentioned fiberglass reinforced fire retardant
The preparation method of nylon composite materials, comprising the following steps: be dried in vacuo the semiaromatic copolymer polyamide resin at 100 DEG C
8~12 hours, semiaromatic copolymer polyamide resin, heat filling, fire retardant, Masterbatch are stirred in high speed agitator then and matched
It is mixed, it is eventually adding in double screw extruder hopper, while the glass fibre being added from double screw extruder side, twin-screw
The temperature of extruder is controlled at 250 DEG C~330 DEG C, obtains semiaromatic copolymer nylon composite material.
The synthetic method of above-mentioned semiaromatic copolymer polyamide resin is the following steps are included: by the binary acid and binary of equimolar amounts
Amine, catalyst, lubricant, deionized water are added in the high-temperature high-pressure reaction kettle of 10L, displace air in kettle with High Purity Nitrogen,
Successively three times, and retain nitrogen pressure 0.15MPa；Open stirring, in 1~3 hour, increase temperature to 200 DEG C~225 DEG C,
Reactor pressure is 0.7MPa~2.5MPa at this time, maintains this pressure 0.5~6 hour；It opens vent valve and slowly deflates, in kettle
Temperature rises to 280 DEG C~310 DEG C, is kept for 0~1 hour, and discharging obtains semiaromatic copolymer polyamide resin.
Compared with the prior art, the advantages of the present invention are as follows: semiaromatic copolymer nylon composite material tool prepared by the present invention
Have good cost performance, the semiaromatic copolymer nylon composite material have high fluidity, high intensity, low warpage, it is thermally conductive, can be fire-retardant
The features such as, easy processing molding, excellent combination property, the product casing surface of preparation, and can Quick diffusing device without floating fine phenomenon
Internal heat improves service life.
In addition, the preparation method of semiaromatic copolymer nylon composite material of the invention, step is simple, easy to operate, cost
Low, good product quality can widely promotion and application.
Specific embodiment
To facilitate the understanding of the present invention, present invention work more comprehensively, is meticulously described below in conjunction with preferred embodiment,
But the protection scope of the present invention is not limited to the following specific embodiments.
Unless otherwise defined, all technical terms used hereinafter and the normally understood meaning of those skilled in the art
It is identical.Technical term used herein is intended merely to the purpose of description specific embodiment, is not intended to the limitation present invention
Protection scope.
Unless otherwise specified, various raw material, reagent, the instrument and equipment etc. used in the present invention can pass through city
Field is commercially available or can be prepared by existing method.
Embodiment 1:
A kind of semiaromatic copolymer nylon composite material of the invention mainly processes preparation by the component of following mass fraction
It forms:
33.75 parts of semiaromatic copolymer polyamide resin；
40 parts of glass fibre；
15 parts of heat filling
1 part of Masterbatch；
10.25 parts of composite flame-retardant agent.
Synthon: terephthalic acid (TPA) (1554g), hexamethylene diamine (1090g), caprolactam (1360g), lubricant P12
(12g) is the 0.3% of synthon quality, and deionized water (1300g) is added in the high-temperature high-pressure reaction kettle of 10L, and use is high-purity
Nitrogen displaces air in kettle, successively three times, and retains nitrogen pressure 0.15MPa；Stirring is opened, in 1.5 hours, increases temperature
To 210 DEG C, reactor pressure is 1.8MPa at this time, maintains this pressure 4 hours；It opens vent valve and slowly deflates, temperature in the kettle
285~290 DEG C are risen to, 20min is kept, discharging obtains semiaromatic copolymer nylon 6T/6.
At 272 DEG C, relative viscosity is controlled 2.1 for the fusing point control of the semiaromatic copolymer polyamide resin.On in the present embodiment
The glass fibre stated is flat glass fiber, and section is pancake, the size of the main cross section axis in section and time cross section axis
Ratio is 3.5, and the chopped length of glass fibre is 3.0mm；The monofilament of glass fibre is with a thickness of 8~9 μm.It is above-mentioned in the present embodiment
Heat filling be galapectite.Above-mentioned fire retardant is diethyl hypo-aluminum orthophosphate (OP1230) in the present embodiment, and fire retardant rises
Beginning decomposition temperature is greater than 300 DEG C.0.25 part of zinc borate is also added in fire retardant.
The preparation method of the thermally conductive semiaromatic copolymer nylon composite material of the above-mentioned fiberglass reinforced fire retardant of the present embodiment is specific to wrap
It includes following steps: semiaromatic copolymer polyamide resin being dried in vacuo 12 hours at 100 DEG C, then by the half of above-mentioned mass fraction
Fragrant copolymer polyamide resin, fire retardant, heat filling and Masterbatch stir compounding in high speed agitator, are eventually adding twin-screw
In extruder hopper, while the glass fibre of above-mentioned mass fraction being added from double screw extruder side, double screw extruder
Temperature control at 260 DEG C~295 DEG C, specific 1st~9 area temperature is successively are as follows: 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 are 285 DEG C；It is mediated under conditions of revolving speed 250r/min, obtains glass and increase
Strong fire-retardant semiaromatic copolymer nylon composite material.By to the composite products and carrying out mechanical property, mobility, leading
The test of hot, anti-flammability, warpage, appearance, acquired results are listed in the table below in 1.
Embodiment 2:
The proportion of the semiaromatic copolymer nylon composite material of the present embodiment is substantially the same manner as Example 1, the operation step of preparation
Rapid and technological parameter condition is also substantially the same manner as Example 1, distinguishes in the semiaromatic copolymer nylon selected in this present embodiment
Resin is PA6T/66, and fusing point is 271 DEG C, relative viscosity 2.12.The performance indexes of the present embodiment composite material see
The following table 1.
Semiaromatic copolymer polyamide resin is the synthetic method of PA6T/66 the following steps are included: will be to benzene two in the present embodiment
Formic acid (824g), 1,6- hexamethylene diamine (580g), nylon salt (2600g) and lubricant P12 (12g), deionized water (1300g)
It is added in the high-temperature high-pressure reaction kettle of 10L, displaces air in kettle with High Purity Nitrogen, successively three times, and retain nitrogen pressure
0.15MPa；Stirring is opened, in 1.5 hours, increases temperature to 210 DEG C, reactor pressure is 1.8MPa at this time, maintains this pressure
Power 1 hour；It opens vent valve and slowly deflates, temperature in the kettle rises to 285 DEG C~290 DEG C, keeps 20min, and discharging obtains half virtue
Fragrant copolymer polyamide resin PA6T/66.
Embodiment 3:
The proportion of the semiaromatic copolymer nylon composite material of the present embodiment is substantially the same manner as Example 1, the operation step of preparation
Rapid and technological parameter condition is also substantially the same manner as Example 1, distinguishes in the semiaromatic copolymer nylon selected in this present embodiment
Resin is PA6T/66/6, and for synthesis technology with embodiment 1, synthon is terephthalic acid (TPA), hexamethylene diamine, nylon salt, acyl in oneself
Amine, lubricant P12 are the 0.3% of synthon, and fusing point is 270 DEG C, relative viscosity 2.11.The present embodiment composite material
Performance indexes is see the following table 1.
Embodiment 4:
The proportion of the semiaromatic copolymer nylon composite material of the present embodiment is substantially the same manner as Example 1, the operation step of preparation
Rapid and technological parameter condition is also substantially the same manner as Example 1, distinguishes in the semiaromatic copolymer nylon selected in this present embodiment
Resin is PA6T/6I/6, and for synthesis technology with embodiment 1, synthon is terephthalic acid (TPA), hexamethylene diamine, nylon salt, acyl in oneself
Amine, lubricant P12 are the 0.3% of synthon, and fusing point is 273 DEG C, relative viscosity 2.13.The present embodiment composite material
Performance indexes is see the following table 1.
Embodiment 5:
The proportion of the semiaromatic copolymer nylon composite material of the present embodiment is substantially the same manner as Example 1, the operation step of preparation
Rapid and technological parameter condition is also substantially the same manner as Example 1, distinguishes in the semiaromatic copolymer nylon selected in this present embodiment
Resin is PA10T/6, and for synthesis technology with embodiment 1, synthon is terephthalic acid (TPA), hexamethylene diamine, nylon salt, acyl in oneself
Amine, lubricant P12 are the 0.3% of synthon, and the performance indexes of the present embodiment composite material is see the following table 1.
Table 1: the performance detection parameter of each embodiment product
Comparative example 6:
The main component and proportion of the semiaromatic copolymer nylon composite material of the present embodiment are substantially the same manner as Example 1,
Difference is PA6T/6 in the semiaromatic copolymer polyamide resin selected in this present embodiment, and fusing point is 295 DEG C, and relative viscosity is
2.1；In addition, the operating procedure and technological parameter condition of the preparation of the present embodiment product are also substantially the same manner as Example 1, difference is only
Be: the temperature of double screw extruder is controlled at 280 DEG C~315 DEG C, and specific 1st~9 area temperature is successively are as follows: 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 are 305 DEG C.The present embodiment composite material
Performance indexes is see the following table 2.
Comparative example 7:
The main component and proportion of the semiaromatic copolymer nylon composite material of the present embodiment are substantially the same manner as Example 1, system
Standby operating procedure and technological parameter condition is also substantially the same manner as Example 1, and difference is only that: half virtue that the present embodiment is selected
The relative viscosity of fragrant copolymer polyamide resin PA6T/6 is 2.7, and the performance indexes of the present embodiment composite material is see the following table 2.
Comparative example 8:
The main component and proportion of the semiaromatic copolymer nylon composite material of the present embodiment are substantially the same manner as Example 1, system
Standby operating procedure and technological parameter condition is also substantially the same manner as Example 1, and difference is only that: the glass that the present embodiment is selected
Fiber is the glass fibre in typical circular section, and the performance indexes of the present embodiment composite material is see the following table 2.
Comparative example 9:
The main component and proportion of the semiaromatic copolymer nylon composite material of the present embodiment are substantially the same manner as Example 1, system
Standby operating procedure and technological parameter condition is also substantially the same manner as Example 1, and difference is only that: half virtue of synthesis in the present embodiment
Lubricant is not added with when fragrant copolymer nylon, the performance indexes of the present embodiment composite material is see the following table 2.
Comparative example 10:
48.75 parts of semiaromatic copolymer polyamide resin；
40 parts of glass fibre；
1 part of Masterbatch；
10.25 parts of composite flame-retardant agent
The semiaromatic copolymer polyamide resin of the present embodiment is the same as embodiment 1, the semiaromatic copolymer nylon composite wood of the present embodiment
Expect that operating procedure and the technological parameter condition of preparation are also substantially the same manner as Example 1, difference is: being not added in the present embodiment
Heat filling, semi-aromatic nylon resin increase to 48.75 parts, and the performance indexes of the present embodiment composite material is see the following table 2.
Table 2: the performance test results of each product in comparative example
Comparison by above-mentioned Tables 1 and 2 is it is found that the fusing point of semiaromatic copolymer nylon is excessively high or relative viscosity is excessively high, again
The mobility of condensation material is deteriorated and has floating fine phenomenon；Circular glass fiber is selected, obtained composite material warpage is obvious and has floating
It is fine；Do not add lubricant when polymerization, the mobility of composite material is deteriorated and has a small amount of floating fibre；Not plus Heat Conduction Material, composite material
Thermal coefficient reduces.Optimal processing parameter is as follows: adding 0.3% lubricant to prepare semiaromatic copolymer nylon, and controls its fusing point
In 270 DEG C~275 DEG C, relative viscosity range in 2.0~2.2,40% flat glasses, 15% heat filling, 10% fire retardant.It can
The semiaromatic copolymer nylon composite material of the characteristics such as the high flowing of preparation, high-strength, low warpage, thermally conductive, fire-retardant.
In above embodiments, the test method and standard of each performance parameter are as follows:
1. relative viscosity [η]
The semiaromatic copolymer polyamide resin of test is dissolved in the concentrated sulfuric acid, obtaining concentration is 1g/dl, is measured at 25 DEG C
The relative viscosity η r of solution:
η r=t1/t0；
Wherein t0 indicate solvent outflow time (s), t1 indicate sample solution outflow time (s), η r be equal to solution with
The ratio of solvent delivery time.
2. fusing point
Using plum Teller-support benefit DSC1 Instrument measuring sample fusing point, under nitrogen atmosphere, risen from room temperature with 10 DEG C/minute
Temperature keeps 5min to 330 DEG C, room temperature when then cooling with 10 DEG C/minute of speed, then is warming up to 330 with 10 DEG C/minute of speed
DEG C, endotherm peak temperature at this time is melting point polymer.
3. mechanical property
The composite material of preparation is molded test bars, tensile strength is tested according to standard GB/T1040.2-2006, according to mark
It is strong to test Charpy Impact according to standard GB/T1043.1-2008 for quasi- GB/T9341-2008 test bending strength and bending modulus
Degree.
4. mobility
Melt index is tested according to standard GB/T3682-2000, test temperature is higher than 30 DEG C of melting point resin, and load load is
2.16kg。
5. electrical conductivity
According to standard ASTM D5470 testing conductive coefficient.
6. anti-flammability
It is tested according to standard UL94:2014 using the batten of 1.6mm thickness, sample is adjusted under 23 DEG C, 50% relative humidity
It is tested after 96 hours.
7. warpage
It will be placed on platform having a size of 100mm × 100mm × 1mm injection molding sheet coupon, be 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 the other side.
8. appearance
It is molded 5mm × 5mm × 1mm sample, the floating fine situation of specimen surface is observed by Electronic Speculum.
Claims (8)
1. a kind of thermally conductive semiaromatic copolymer nylon composite material of fiberglass reinforced fire retardant, which is characterized in that it is mainly by following quality
The component processing of score is prepared:
Semiaromatic copolymer polyamide resin 25%~50%；
Glass fibre 25%~55%；
Heat filling 10%~25%；With
Fire retardant 6%~20%；
Wherein, the fusing point control of the semiaromatic copolymer polyamide resin is at 270 DEG C~275 DEG C, relative viscosity control 2.0~
2.2, and contain lubricant in the raw material of the semiaromatic copolymer polyamide resin, the additive amount control of the lubricant exists
0.05wt%~1wt%；The glass fibre is flat glass fiber, and section is pancake, the main cross section in the section
The dimensional ratios of axis and time cross section axis are 1.5~6；The chopped length of the glass fibre is 2~6mm；The glass fibre
Monofilament with a thickness of 7~10 μm.
2. the thermally conductive semiaromatic copolymer nylon composite material of fiberglass reinforced fire retardant according to claim 1, which is characterized in that its
Mainly it is prepared by the component processing of following mass fraction:
Semiaromatic copolymer polyamide resin 30%~40%；
Glass fibre 30%~45%；
Heat filling 12%~20%；With
Fire retardant 7%~15%.
3. the thermally conductive semiaromatic copolymer nylon composite material of fiberglass reinforced fire retardant according to claim 2, which is characterized in that its
Mainly it is prepared by the component processing of following mass fraction:
Semiaromatic copolymer polyamide resin 32%~38%；
Glass fibre 35%~42%；
Heat filling 14%~18%；With
Fire retardant 8%~12%.
4. the thermally conductive semiaromatic copolymer nylon composite material of fiberglass reinforced fire retardant described in any one of claim 1 to 3,
It is characterized in that, the synthon of the semiaromatic copolymer polyamide resin is aromatic acid, aliphatic dibasic acid, aliphatic two
First amine, lactams, amino carboxylic acid.
5. the thermally conductive semiaromatic copolymer nylon composite material of fiberglass reinforced fire retardant according to claim 4, it is characterised in that:
The aromatic acid is terephthalic acid (TPA), M-phthalic acid, 2- methylterephthalic acid, 2,5- dichloro terephthaldehyde
Acid, 2,6- naphthalene diacid, 2,7- naphthalene diacid, 1,4- naphthalene diacid, 4,4 '-biphenyl dicarboxylic acids, diphenyl methane -4,4 '-dicarboxylic acids, two
One or more of phenylsulfone -4,4 '-dicarboxylic acids；
The aliphatic dibasic acid is malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, the last of the ten Heavenly stems two
Acid, dimethyl malonic acid, 3,3- diethyl succinic acid, 2- methyl adipic acid, 2,2- dimethylated pentanedioic acid, 1,3- pentamethylene dicarboxyl
One or more of acid and 1,4- cyclohexane dicarboxylic acid；
The aliphatic diamine be 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 diamines, 1,12- dodecamethylene diamine, 1,13- tridecane diamine, 2- methyl-1,5- penta 2
Amine, 2,2,4- trimethyl -1,6- hexamethylene diamine and 2- methyl-1, one or more of 8- octamethylenediamine；
The lactams is caprolactam and/or lauric lactam；
The amino carboxylic acid be omega-amino caproic acid, omega-amino n-nonanoic acid, omega-amino undecanoic acid, in omega-amino lauric acid/dodecanoic acid at least
It is a kind of；
The lubricant be erucyl amide, oleamide, ethylene bis-fatty acid amides, silicone, in lignite acid derivative extremely
Few one kind.
6. the thermally conductive semiaromatic copolymer nylon composite material of fiberglass reinforced fire retardant described in any one of claim 1 to 3,
It is characterized in that, the fire retardant is hypophosphites；The initial decomposition temperature of fire retardant is greater than 300 DEG C；Also contain in the fire retardant
There is zinc borate, additive amount is the 1%~5% of the weight of fire retardant.
7. the thermally conductive semiaromatic copolymer nylon composite material of fiberglass reinforced fire retardant described in any one of claim 1 to 3,
It is characterized in that, the heat filling is micron order or alumina in Nano level, magnesia, zinc oxide, aluminium nitride, galapectite, nitridation
At least one of boron, silicon carbide.
8. a kind of such as the thermally conductive semiaromatic copolymer nylon composite material of fiberglass reinforced fire retardant according to any one of claims 1 to 7
Preparation method, comprising the following steps: the semiaromatic copolymer polyamide resin is dried in vacuo 8~12 hours at 100 DEG C, so
Semiaromatic copolymer polyamide resin, fire retardant, heat filling, Masterbatch are stirred to compounding in high speed agitator afterwards, are eventually adding
In double screw extruder hopper, while the glass fibre being added from double screw extruder side, the temperature of double screw extruder
Degree control obtains the thermally conductive semiaromatic copolymer nylon composite material of fiberglass reinforced fire retardant at 250 DEG C~330 DEG C.
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| CN109354863B (en) * | 2018-09-29 | 2021-08-03 | 辰东意普万新材料(广东)有限公司 | Copolymerized nylon product and preparation method thereof |
| CN109912968B (en) * | 2019-02-26 | 2021-09-28 | 西安西电电气研究院有限责任公司 | Nano-alumina and glass fiber synergistic composite reinforced nylon material and preparation method thereof |
| CN110483992B (en) * | 2019-09-04 | 2021-11-16 | 株洲时代新材料科技股份有限公司 | Low-warpage reinforced semi-aromatic high-temperature nylon composite material and preparation method thereof |
| CN110982258A (en) * | 2019-12-28 | 2020-04-10 | 江苏博云塑业股份有限公司 | Floating-fiber-free high-glass-fiber-reinforced nylon material and preparation method thereof |
| CN113372716A (en) * | 2021-07-09 | 2021-09-10 | 浙江谱奈图新材料科技有限公司 | Halogen-free flame-retardant nylon material and preparation method thereof |
| CN113429783A (en) * | 2021-07-09 | 2021-09-24 | 浙江谱奈图新材料科技有限公司 | Low-friction low-abrasion high-temperature nylon and preparation method thereof |
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