CN109852051A - A kind of nylon/polyphenylene sulfide alloy material and preparation method thereof - Google Patents
A kind of nylon/polyphenylene sulfide alloy material and preparation method thereof Download PDFInfo
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- CN109852051A CN109852051A CN201811621687.5A CN201811621687A CN109852051A CN 109852051 A CN109852051 A CN 109852051A CN 201811621687 A CN201811621687 A CN 201811621687A CN 109852051 A CN109852051 A CN 109852051A
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Abstract
The invention discloses a kind of nylon/polyphenylene sulfide alloy materials and preparation method thereof, include component: 35-80 parts of nylon, 1-10 parts of polyphenylene sulfides, 20-50 parts of glass fibres.The present invention is in nylon resin by adding a certain proportion of polyphenylene sulfide, pass through fiberglass reinforced again, nylon/the polyphenylene sulfide alloy material being prepared, the enhancing nylon material modified compared to common laser mark agent, is not only able to maintain preferable mechanical performance, while having excellent laser marking performance, and heavy metal component is not contained, environmental protection, it is pollution-free, it is conducive to color matching.Alloy material of the invention can in the environment of high temperature and humidity not fugitive color, still there is good laser marking effect, its scope of application is made to obtain bigger extension.
Description
Technical field
The invention belongs to modified nylon technical field, in particular to a kind of nylon/polyphenylene sulfide alloy material and its preparation
Method.
Background technique
Polyamide has excellent mechanical performance, excellent barrier property, heat resistance, wearability, resistant to chemical etching
Etc. excellent comprehensive performance, it is widely used in the fields such as machinery manufacturing industry, electric tool, electronic apparatus and communications and transportation.Especially
In electronic enterprises, many products all use laser marking to identify, this will nylon material have good laser beat
Mark performance.Nylon material, which generally compares, is difficult to mark, and the laser marking effect to obtain relatively good must add laser marking
Agent.
Patent CN201810350929 disclose it is a kind of can laser marking modification of nylon, made by adding laser marking agent
Obtaining nylon has good laser marking effect, but laser marking agent addition is so that the mechanical property of materials declines.Patent
CN1152911C is disclosed a kind of uses the spherical TiO2 particle of tin oxide/antimony coating as laser additive using defined particle size
Method, but this laser marking agent contains this non-environmental protection substance of antimony oxide.Patent CN102762658B is disclosed
A kind of laser-markable composition is added by polymer of the addition containing butadiene and the laser direct forming containing copper
Agent, Lai Gaishan material laser mark effect, but the laser marking effect of this cupric is easy in the environment of high temperature and humidity
It fades.Patent CN 101395007A discloses a kind of laser-markable composition, and the laser marking agent used is acrylic acid
The polymer or metal sulfate of ester monomer, can obtain preferable laser marking effect, but this laser marking agent true qualities
It is a kind of dark matter, is only applicable to dark product, is unfavorable for light-coloured prods.
From current a large amount of document and patent retrieval it can be found that most technologies are all by adding certain proportion
Laser marking agent, that is, laser carving powder, the laser marking effect of Lai Tigao material.The advantages of technology is to implement simply, no
Foot is that laser marking agent cost is often costly, the improper mechanical performance that will affect material of adding proportion, while many laser
Mark agent has the ingredient of heavy metal, both pollutes environment, is also easy to produce color dirt, is unfavorable for realizing color matching.
Summary of the invention
To overcome the problems of the above-mentioned prior art, the purpose of the present invention is to provide a kind of nylon/polyphenylene sulfides to close
Golden material, which is not only able to maintain preferable mechanical performance, but also has excellent laser marking performance.
The purpose of the present invention is realized by following proposal:
A kind of nylon/polyphenylene sulfide alloy material, according to parts by weight, including following component:
35-80 parts of nylon；
1-10 parts of polyphenylene sulfide；
20-50 parts of glass fibre.
The nylon, also referred to as polyamide, selected from by polycondensation at least one aliphatic dicarboxylic acid and aliphatic diamine or
The polyamide that person's ring diamines obtains, such as PA66, PA610, PA612, PA1212, PA46, MXD6, or pass through polycondensation at least one
The polyamide that kind aromatic dicarboxylic acid and aliphatic diamine obtain, such as according to terephthalamide, according to isophtalamide, poly- virtue
Amide or their mixture and copolyamide.Polyamide of the invention be also selected from through at least one amino acid or
The polycondensation of lactams with itself polyamide obtained, the amino acid can be generated by the hydrolysis of lactam nucleus,
Such as PA6, PA7, PA11, PA12 or their mixture and copolyamide.In the present invention, nylon resin can be independent
Using only one of above-mentioned polyamide, two kinds or more, preferably PA66 can also be applied in combination
The glass fibre is the glass fibre from the following group using at least one type: E glass, H glass, R, S glass, D
Glass, C glass and quartz glass, particularly preferably use the glass fibre made of E glass.The diameter of the glass fibre
It is 9-16 μm, preferably 10-12 μm.
According to actual performance needs, nylon/polyphenylene sulfide alloy material of the invention further includes according to parts by weight 0.1
~1 part of antioxidant, 0.1~1 part of lubricant.
The antioxidant is alkali metal or alkaline-earth hypophosphites, phosphite ester, phosphinate and its mixture.
The lubricant is higher fatty acids, higher fatty acid metal salt, high-grade aliphatic ester or higher fatty acid amides
One or more of mixing.
As the higher fatty acids, be not limited to following substance, can enumerate for example: stearic acid, palmitinic acid, behenic acid,
Saturated or unsaturated, linear chain or branched chain the fat of the carbon atom numbers such as erucic acid, oleic acid, lauric acid and montanic acid 8~40
Race's monocarboxylic acid etc..In these substances, from inhibit melt-processed when gas generate, inhibit processing and forming when mold in mold deposit
From the viewpoint of, preferably stearic acid, montanic acid.
The higher fatty acid metal salt refers to the metal salt of higher fatty acids.As constitute metal salt metallic element,
The first, second, third race of preferred elements periodic table element, zinc and aluminium etc., more preferable calcium, sodium, potassium, magnesium etc..As described advanced
Fatty acid metal salts are not limited to following substance, can enumerate for example: calcium stearate, aluminum stearate, zinc stearate, magnesium stearate,
Montanic acid calcium, montanic acid sodium, calcium palmitate etc..In these substances, is generated from gas when inhibiting melt-processed, molding is inhibited to add
From the viewpoint of mold deposit in working hour mold, the preferably metal salt of montanic acid and stearic metal salt.
The high-grade aliphatic ester refers to the carboxylate of higher fatty acids and alcohol.Wherein, from gas when inhibiting melt-processed
Body generates, when inhibiting processing and forming from the viewpoint of mold deposit in a mold, preferably the aliphatic carboxylic acid of carbon atom number 8~40 with
The ester of the aliphatic alcohol of carbon atom number 8~40.Here, above-mentioned fatty acid can be used as higher fatty acids.As aliphatic
Alcohol is not limited to following substance, can enumerate for example: stearyl alcohol, behenyl alcohol, laruyl alcohol etc..As high-grade aliphatic ester, it is not limited to
Following substance can be enumerated for example: stearyl stearate, behenic acid Shan Yu ester etc..
The higher fatty acid amides refer to the amide compound of higher fatty acids.It is unlimited as higher fatty acid amides
In following
Substance can be enumerated for example: stearmide, oleamide, erucic amide, ethylenebisstearamide, ethylenebisoleoamide,
N- stearyl stearamide, N- stearyl erucic amide etc..In these substances, generates, inhibits from gas when inhibiting melt-processed
From the viewpoint of mold deposit when processing and forming in mold, preferably stearmide, erucic amide, ethylenebisstearamide, N- are stearic
Base erucic amide, more preferable ethylenebisstearamide, N- stearyl erucic amide.
These higher fatty acids, higher fatty acid metal salt, high-grade aliphatic ester and high fatty acid amide, respectively can be single
One kind is solely used only, can also be used in combination.
The invention also discloses the preparation methods of above-mentioned nylon/polyphenylene sulfide alloy material, include the following steps:
Each raw material is proportionally weighed, is pre-mixed to obtain pre-composition in high mixer, pre-composition is then put into twin-screw
Melting mixing, and extruding pelletization are carried out in extruder, obtain nylon/polyphenylene sulfide alloy material；Wherein, twin-screw extrusion
The screw slenderness ratio of machine is 40 ~ 48:1, and barrel temperature is 270 ~ 300 DEG C, and screw speed is 200 ~ 550rpm.
The present invention also provides polyphenylene sulfides to improve the application in nylon composite laser marking performance, with nylon combination
Object total weight, the weight content of polyphenylene sulfide are 1-10%.
The present invention compared with the existing technology, have the following advantages and the utility model has the advantages that
(1) present invention passes through in nylon resin adds a certain proportion of polyphenylene sulfide, then by fiberglass reinforced, is prepared into
Nylon/the polyphenylene sulfide alloy material arrived, the enhancing nylon material modified compared to common laser mark agent, is not only able to maintain preferably
Mechanical performance, while there is excellent laser marking performance, and do not contain heavy metal component, environmental protection is pollution-free, conducive to matching
Color.
(2) nylon/polyphenylene sulfide alloy material of the present invention can in the environment of high temperature and humidity not fugitive color, still have
Good laser marking effect, makes its scope of application obtain bigger extension.
Specific embodiment
Further illustrate that the present invention, following specific embodiments are this with comparative example combined with specific embodiments below
Preferable embodiment is invented, but embodiments of the present invention are not limited by following embodiments, are especially not limited to down
State the model of each component raw material used in specific embodiment.
Each component raw material used in the present invention are as follows:
PA66 resin: PA66 EP-158, Zhejiang Hua Feng group；
PA6 resin: PA6 HY2800A, Haiyang chemical fibre；
PPS resin: PPS 1150C, Zhejiang are new and at Materials Co., Ltd；
Glass fibre: ECS301HP-3,11 μm of diameter, Chongqing Polycomp International Co., Ltd；
Antioxidant: N, N'- be bis--(3- (3,5- di-tert-butyl-hydroxy phenyl) propiono) hexamethylene diamine (IRGANOX 1098), bar
Si Fu；
Lubricant: geoceric acid stearyl alcohol ester, LOXIOL G32, German Corning；
Laser marking agent: FABULASE 361；
Performance test standard or method:
1) tensile strength, sample size and testing standard refer to ISO 527-2, rate of extension 10mm/min.Dry state stretches strong
Degree is that standard is molded batten test result after 23 DEG C/50%RH status adjustment 48h；
2) bending strength, sample size and testing standard refer to ISO 178, load on rate 2mm/min.Dry state bending strength
Batten test result after 23 DEG C/50%RH status adjustment 48h is molded for standard；
3) bending modulus, sample size and testing standard refer to ISO 178, load on rate 2mm/min.Dry state bending modulus
Batten test result after 23 DEG C/50%RH status adjustment 48h is molded for standard；
4) IZOD notch impact strength, sample size and testing standard refer to ISO 180.Dry state IZOD notch impact strength is mark
Quasi- injection molding batten test result after 23 DEG C/50%RH status adjustment 48h；
5) laser marking recruitment evaluation, sample size 60mm*60mm*2mm, on infrared laser marking machine, laser beam is according to 18A
Current energy, beat the solid circles that diameter is 20mm, then compare solid circles and other non-laser mark positions of sample
Value of chromatism △ E.The laser labelling △ E of hygrometric state refers to after boiling 3 hours, takes the sample after laser marking in 95 DEG C of water baths
Batten test result after 23 DEG C/50%RH status adjustment 48h out；
6) heavy metal element is analyzed: inductive coupling plasma emission spectrograph (ICP-OES) carries out elemental analysis.
Embodiment 1-8 and comparative example 1-3:
According to comparative example 1 ~ 3 described in table 1 and 1 ~ 8 formulation dosage of specific embodiment weigh respectively PA66 resin, PA6 resin,
PPS, glass, antioxidant and lubricant, and above-mentioned each component is put into mixing machine and carries out mixing until uniformly, being premixed
Object；Then gained pre-composition is put into double screw extruder and carries out melting mixing, and extruding pelletization, obtain PA66/PPS alloy
Material；Wherein the screw slenderness ratio of double screw extruder be 40 ~ 48:1, barrel temperature be 270 ~ 300 DEG C, screw speed be 300 ~
450rpm.Alloy material is tested for the property, test result is as shown in table 2:
1 comparative example 1 ~ 3 of table and 1 ~ 8 dosage of each component of embodiment (parts by weight)
2 the performance test results of table
From embodiment 1-8 and comparative example 1 and 3 as can be seen that the PPS of 1-10 parts of addition can significantly improve the laser marking of material
Effect, color difference △ E is compared to improving 20-40 times before addition, and with the raising of PPS adding proportion, laser marking effect is also gradually
It is promoted；
From embodiment 1 and comparative example 2 as can be seen that although laser marking agent can obtain relatively good laser marking effect,
It is the problem of laser labelling will appear colour fading in the environment of high temperature and humidity, and adds PPS both and can obtain good laser and beat
Mark effect, and can in the environment of high temperature and humidity not fugitive color；On the other hand, laser marking agent addition 1%, mechanical performance
It is decreased obviously, but PPS adding proportion, in the range of 1-10 parts, mechanical performance conservation rate is fine；Moreover, being examined in comparative example 2
Measure the heavy metal (the Cu element of 7800ppm) of higher proportion.
In conclusion PA/PPS alloy material of the invention, possess than commonly enhancing the better laser marking of nylon material
Performance is allowed to especially suitable for plastic products under high temperature, high humidity work condition environment, such as electric equipment products, outdoor equipment field.
Claims (9)
1. a kind of nylon/polyphenylene sulfide alloy material, it is characterised in that: include following components according to parts by weight:
35-80 parts of nylon；
1-10 parts of polyphenylene sulfide；
20-50 parts of glass fibre.
2. nylon/polyphenylene sulfide alloy material according to claim 1, it is characterised in that: the nylon, which is selected from, passes through contracting
Gather the polyamide of at least one aliphatic dicarboxylic acid and aliphatic diamine or the acquisition of ring diamines, by at least one virtue of polycondensation
The polyamide that fragrant race's dicarboxylic acids and aliphatic diamine obtain or the polycondensation by least one amino acid or lactams with itself
Polyamide obtained, preferably polyamide 66.
3. nylon/polyphenylene sulfide alloy material according to claim 1, it is characterised in that: the glass fibre be using
The glass fibre from the following group of at least one type: E glass, H glass, R, S glass, D glass, C glass and quartz glass are special
Not preferably with the glass fibre made of E glass.
4. nylon/polyphenylene sulfide alloy material according to claim 1, it is characterised in that: the diameter of the glass fibre
It is 9-16 μm, preferably 10-12 μm.
5. nylon/polyphenylene sulfide alloy material according to claim 1, it is characterised in that: according to parts by weight, further include
0.1~1 part of antioxidant, 0.1~1 part of lubricant.
6. nylon/polyphenylene sulfide alloy material according to claim 5, it is characterised in that: the antioxidant is alkali metal
Or alkaline-earth hypophosphites, phosphite ester, phosphinate and its mixture；The lubricant is higher fatty acids, height
The mixing of one or more of grade fatty acid metal salts, high-grade aliphatic ester or higher fatty acid amides.
7. a kind of preparation method of nylon/polyphenylene sulfide alloy material of any of claims 1-6, feature exist
In: include the following steps:
Each raw material is proportionally weighed, is pre-mixed to obtain pre-composition in high mixer, pre-composition is then put into twin-screw
Melting mixing, and extruding pelletization are carried out in extruder, obtain nylon/polyphenylene sulfide alloy material；Wherein, double screw extruder
Screw slenderness ratio is 40 ~ 48:1, and barrel temperature is 270 ~ 300 DEG C, and screw speed is 200 ~ 550rpm.
8. polyphenylene sulfide is improving the application in nylon composite laser marking performance.
9. application according to claim 8, which is characterized in that with nylon composite total weight, the weight of polyphenylene sulfide
Content is 1-10%.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811621687.5A CN109852051B (en) | 2018-12-28 | 2018-12-28 | Nylon/polyphenylene sulfide alloy material and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811621687.5A CN109852051B (en) | 2018-12-28 | 2018-12-28 | Nylon/polyphenylene sulfide alloy material and preparation method thereof |
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| CN109852051A true CN109852051A (en) | 2019-06-07 |
| CN109852051B CN109852051B (en) | 2022-03-29 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111155204A (en) * | 2020-01-07 | 2020-05-15 | 重庆普力晟新材料有限公司 | Preparation method of modified polyphenylene sulfide fiber |
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| CN103849144A (en) * | 2012-12-03 | 2014-06-11 | 合肥杰事杰新材料股份有限公司 | Polyphenylene sulfide/nylon alloy material and preparation method thereof |
| US20180065392A1 (en) * | 2015-02-20 | 2018-03-08 | Sabic Global Technologies B.V. | Light colored thermally conductive polymer compositions with laser marking function |
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2018
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| CN103387745A (en) * | 2012-05-10 | 2013-11-13 | 合肥杰事杰新材料股份有限公司 | Flame-retardant glass-fiber reinforced polyamide/polyphenylene sulfide alloy material and preparation method thereof |
| CN103849144A (en) * | 2012-12-03 | 2014-06-11 | 合肥杰事杰新材料股份有限公司 | Polyphenylene sulfide/nylon alloy material and preparation method thereof |
| US20180065392A1 (en) * | 2015-02-20 | 2018-03-08 | Sabic Global Technologies B.V. | Light colored thermally conductive polymer compositions with laser marking function |
| CN108424642A (en) * | 2018-04-18 | 2018-08-21 | 佛山市南海和琦润高分子材料有限公司 | One kind can laser engraving fire-retardant nylon PA66 materials and preparation method thereof |
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| CN111155204A (en) * | 2020-01-07 | 2020-05-15 | 重庆普力晟新材料有限公司 | Preparation method of modified polyphenylene sulfide fiber |
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