CN102732018A - Nylon 66 composite and preparation method thereof - Google Patents
Nylon 66 composite and preparation method thereof Download PDFInfo
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- CN102732018A CN102732018A CN2012102271899A CN201210227189A CN102732018A CN 102732018 A CN102732018 A CN 102732018A CN 2012102271899 A CN2012102271899 A CN 2012102271899A CN 201210227189 A CN201210227189 A CN 201210227189A CN 102732018 A CN102732018 A CN 102732018A
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Abstract
The invention discloses a nylon 66 composite and a preparation method thereof. The specific formula of the nylon 66 composite comprises the following components: 40%-80% of nylon PA66, 10%-40% of inorganic filler, 10%-20% of nano ceramic power, 0-1% of antioxidant, 0-5% of tinting pigment, and 0-0.5% of lubricating auxiliary agent. According to the invention, nano ceramic power is added into nylon PA66, so that the nylon 66 composite can obtain a better rigidity effect. The method for preparing the high-temperature nylon 66 composite adopts screw extrusion or hot press molding, so that the process is simple.
Description
Technical field
The invention belongs to chemical polymeric material field, specially refer to a kind of nylon 66 composition and preparation method thereof.
Background technology
Nylon 66 has good thermotolerance, chemical proofing, intensity and easy to process etc., thereby obtains number of applications at automotive industry, electronic apparatus industry, mechanical means and daily necessities.
Existing P A66 compsn; In order to improve its rigidity; Usually through adding mineral filler such as talcum powder, mica powder, kaolin etc., play nucleogenesis, the percent crystallinity of nylon 66 composition is improved through adding mineral filler; Right talcum powder, mica powder or kaolin are bigger in the amount of the use that improves nylon 66 composition, and rigidity is improved DeGrain.
Summary of the invention
In view of the above, the present invention is necessary to provide a kind of nylon 66 composition with favorable rigidity.
Technical solution of the present invention is: a kind of nylon 66 composition, and it comprises the component of following weight percent proportioning:
PA66：50-80wt%
Mineral filler: 10-40wt%;
Nano-ceramic powder: 10-20wt%;
Oxidation inhibitor: 0-1wt%;
Tinting pigment: 0-5wt%; And
Lubricating auxiliary agent: 0-0.5wt%.
Wherein, rigidity, temperature tolerance and the dimensional stability of the compsn that said mineral filler makes in order to raising, mineral filler comprises talcum powder, mica powder, kaolin etc., granularity is at the 300-500 order.
Wherein, said nano-ceramic powder is the stupalith that utilizes the nanotechnology exploitation, and its particle diameter is in the 1-100 nanometer.Nano-ceramic powder comprises nanometer ZrO
2Ceramic powder, nano-TiO
2Ceramic powder, nanometer AL
2O
3Ceramic powder, nanometer 3Y-TZP ceramic powder, nanometer PTCR ceramic powder or silicon-based nano ceramic powder.Nanometer AL
2O
3And ZrO
2Temperature agglomerating pottery lower has very HS, wherein uses nanometer AL
2O
3Ceramic powder is a matrix, utilizes its fine and close speed fast, the low and good interface ductility of sintering temperature, and the control particle size can obtain to have super good superplastic nano ceramic material at the optimum range of 20-50 nanometer in sintering process.Therefore, nano-ceramic powder increases substantially the rigidity and the superplasticity of the nylon 66 composition that makes.
In addition, nano-ceramic powder also has germicidal action, and nano-ceramic powder comprises photocatalyst-type inorganic antibacterial material, metals ion burning type inorganic antibacterial material and rare-earth activated photochemical catalysis composite inorganic anti-biotic material.For the photocatalyst-type inorganic antibacterial material, photocatalytic semiconductor material has TiO
2, ZrO
2, V
2O
3, ZnO, CdS, SeO
2, GaP, SiC etc., in the glaze of pottery, add TiO
2Or the nano material of composition such as ZnO, they can produce conduction band electron and valence band hole under illumination condition, and there is sucking action in the hole to electronics; Have oxidation capacity, have very strong reactive behavior, can react to form with the H2O of surface adsorption or OH ion has the very hydroxyl of strong oxidizing property; Strong oxidizing property by hydroxyl is removed cell killing; And penetrable cytolemma, destroy the toxin that membrane structure, degradation of cell produce, and also can absorb harmful substances in air simultaneously, purify air.
For metals ion burning type inorganic antibacterial material, metals ion mainly is a silver ions, and silver ions and compound thereof have the excellent antibiotic effect.Make antiseptic-germicide with silver ions, glaze with can separate out silver ions after water contacts, directly get into the growth that destroys bacterium in the bacterial body; The anti-microbial effect mechanism of silver type inorganic antiseptic has two kinds, and the one, the antibiotic mechanism of slowly-releasing sterilization of silver ions, the 2nd, active oxygen sterilization mechanism.The antibiotic mechanism of silver ions slowly-releasing sterilization is meant in its use; Antiseptic-germicide slowly discharges Ag+; Because Ag+ can destroy bacterial cell membrane or attract the thin base of zymoprotein in the bacterial body consumingly under lower concentration very; And the activity of the reduction cellular plasm organized enzyme that combines rapidly, have anti-microbial effect.Thereby through slowly-releasing Ag+, inorganic antiseptic can be brought into play persistent antibacterial effect.The antibiotic mechanism of the active oxygen of silver ions shows that the reductibility of high oxidation state silver is high, under the effect of light, under antiseptic-germicide and water or the air, generates active O
-2And XOH, have very strong redoxomorphism.
For rare-earth activated photochemical catalysis composite inorganic anti-biotic material; Be that the nano composite rare earth anti-biotic material is added in the glaze formula of ceramic clay; REE can be oxidized to water the living radical and the negative ion of strong oxidation capacity; When having an effect, reach the purpose of kill bacteria with bacterial cell membrane.
So, the nylon 66 composition that nano-ceramic powder is formed not only rigidity can greatly improve, and can also prevent that the material surface that bacterium is processed at nylon 66 composition from growing.Through experimental verification, through adding a spot of nano-ceramic powder, can not only significantly reduce the add-on of mineral filler, can also significantly improve the rigidity of nylon 66 composition.
Said oxidation inhibitor is used for improving the ability of the thermo oxidative aging of nylon 66 composition, and inhibitor comprises antioxidant CA, antioxidant 1010 or oxidation inhibitor 168 etc.
Said tinting pigment is used to allocate the color and luster of nylon 66 composition, and is blue blue or green blue with phthalein like the available white titanium pigment of white, green with the phthalein viridescent etc., can add the tinting pigment of correspondence according to different needs, and tinting pigment is general commercially available article.
Said lubricating auxiliary agent is in order to improve the oilness of composition article, and lubricating auxiliary agent can be a calcium stearate, ethylene bis stearamide etc.
In addition, the present invention is necessary to provide a kind of preparation method of nylon 66 composition, may further comprise the steps: 1) take by weighing material: PA66:50-80wt%; Mineral filler: 10-40wt%; Nano-ceramic powder: 10-20wt%; Oxidation inhibitor: 0-1wt%; Tinting pigment: 0-5wt%; And lubricating auxiliary agent: 0-0.5wt%.
2) mixture: the above-mentioned material that takes by weighing is joined in the high-speed mixer, mix;
3) extruding pelletization or hot-forming: during through extruding pelletization, mixture inserted in the twin screw extruder extrude, cooling, pelletizing make nylon 66 composition; When hot-forming, pour in the suitable mould heating compression moulding into mixing.
In order to make nylon 66 composition possess preferable rigidity, the present invention can obtain preferable rigidity effect through adding nano-ceramic powder.Through selecting oxidation inhibitor for use, the hot-air aging resistance of material is significantly increased; Through adding tinting pigment, can make goods have required color and color and luster.Nano-ceramic powder also can prevent composition article surface breed bacteria, goods environmentally-friendly sanitary.Through adding lubricating auxiliary agent, improve the oilness and the shock-resistance of composition article.Nylon 66 composition makes through extruding pelletization or hot-forming preparation method.The nylon 66 composition useful application that makes is in industries such as automobile, machinery, electronics, electrical equipment.
Embodiment
Further specify nylon 66 composition of the present invention and preparation method thereof below in conjunction with embodiment and Comparative Examples, and find out that through contrast adding nano-ceramic powder obtains the unusual effect that rigidity improves.Specific embodiment is further explain the present invention, non-limiting protection scope of the present invention.
Comparative Examples 1
PA66 60wt%, talcum powder 35wt%; Antioxidant CA 0.5 wt%, white titanium pigment 4wt% and calcium stearate 0.5 wt%.
Embodiment 1
PA66 60wt%, talcum powder 25 wt%; Nanometer ZrO
2Ceramic powder 10wt%, antioxidant CA 0.5 wt%, white titanium pigment 4wt% and calcium stearate 0.5 wt%.
Embodiment 2
PA66 60wt%, talcum powder 20 wt%; Nanometer ZrO
2Ceramic powder 15wt%, antioxidant CA 0.5 wt%, white titanium pigment 4wt% and calcium stearate 0.5 wt%.
Embodiment 3
PA66 60wt%, talcum powder 15 wt%; Nanometer ZrO
2Ceramic powder 20wt%, antioxidant CA 0.5 wt%, white titanium pigment 4wt% and calcium stearate 0.5 wt%.
Embodiment 4
PA66 60wt%, talcum powder 10 wt%; Nanometer ZrO
2Ceramic powder 25wt%, antioxidant CA 0.5 wt%, white titanium pigment 4wt% and calcium stearate 0.5 wt%.
Embodiment 5
PA66 60wt%, talcum powder 30 wt%; Nanometer ZrO
2Ceramic powder 5wt%, antioxidant CA 0.5 wt%, white titanium pigment 4wt% and calcium stearate 0.5 wt%.
Comparative Examples 2
PA66 50wt%, kaolin 45wt%; Antioxidant CA 0.5 wt%, dark green 4wt% of phthalein and calcium stearate 0.5 wt%.
Embodiment 6
PA66 50wt%, kaolin 35 wt%; Nano-TiO
2Ceramic powder 10wt%, antioxidant CA 0.5 wt%, dark green 4wt% of phthalein and calcium stearate 0.5 wt%.
Embodiment 7
PA66 50wt%, kaolin 30 wt%; Nano-TiO
2Ceramic powder 15wt%, antioxidant CA 0.5 wt%, dark green 4wt% of phthalein and calcium stearate 0.5 wt%.
Embodiment 8
PA66 50wt%, kaolin 25 wt%; Nano-TiO
2Ceramic powder 20wt%, antioxidant CA 0.5 wt%, dark green 4wt% of phthalein and calcium stearate 0.5 wt%.
Embodiment 9
PA66 50wt%, kaolin 20 wt%; Nano-TiO
2Ceramic powder 25wt%, antioxidant CA 0.5 wt%, dark green 4wt% of phthalein and calcium stearate 0.5 wt%.
Embodiment 10
PA66 50wt%, kaolin 40 wt%; Nano-TiO
2Ceramic powder 5wt%, antioxidant CA 0.5 wt%, dark green 4wt% of phthalein and calcium stearate 0.5 wt%.
Comparative Examples 3
PA66 80wt%, talcum powder 15wt%; Antioxidant CA 0.5 wt%, white titanium pigment 4wt% and calcium stearate 0.5 wt%.
Comparative Examples 4
PA66 80wt%, talcum powder 20 wt%.
Embodiment 11
PA66 80wt%, talcum powder 10 wt%; Nanometer V
2O
3Ceramic powder 10wt%, white titanium pigment 4wt% and calcium stearate 0.5 wt%.
Embodiment 12
PA66 80wt%, nanometer ZrO
2Ceramic powder 20wt%.
Each component in above-mentioned each example is mixed back extruding pelletization or hot-forming, promptly get the goods of nylon 66 composition.In embodiment 1-11, with PA66, mineral filler; Impeller mixing 5-10 minute, add oxidation inhibitor then, tinting pigment; Nano-ceramic powder and lubricating auxiliary agent thorough mixing 5-10 minute; Extrude through twin screw extruder then, screw speed is 450r/min, and forcing machine is respectively distinguished temperature between 175-210 ℃.In Comparative Examples 1-3, mix earlier PA66 and mineral filler 5-10 minute, added oxidation inhibitor and lubricating auxiliary agent thorough mixing then 5-10 minute, extrude through twin screw extruder then.
Also can after mixing, insert in the mould after each component is mixed among the foregoing description 1-12 and the Comparative Examples 1-3, add hot pressing and form the nylon 66 composition goods that make correspondence.Composition properties test result that the foregoing description 1-12 and Comparative Examples 1-3 make such as following table 1-3:
Table 1, the performance perameter table of Comparative Examples 1 and embodiment 1-5
Table 2, the performance perameter table of Comparative Examples 2 and embodiment 6-10
Table 3, the performance perameter table of Comparative Examples 3-4 and embodiment 11-12
Can find out from the foregoing description, through Comparative Examples 1 comparative example 1-3, or Comparative Examples 2 comparative example 6-8; Under other ratio of component heavy phases situation together; And, can reduce talcous consumption through adding nano-ceramic powder, can also greatly improve the rigidity of nylon 66 composition.Through embodiment 1-3 comparative example 4-5, or embodiment 6-8 comparative example 9-10, be lower than 10% or surpass at 20% o'clock at nano-ceramic powder, the rigidity of high nylon 66 composition is improved has limitation.To sum up, the nylon 66 composition that the present invention obtains is significantly improved in performances such as tensile strength, socle girder notched Izod impact strength and flexural strengths through adding nano-ceramic powder.Preferable coordinating effect has also been played in other each components and PA66 combination.And through adding nano-ceramic powder, not only improved the rigidity of nylon 66 composition, also prevented composition article surface breed bacteria, the goods environmentally-friendly sanitary.Through adding tinting pigment, make composition article have required color and color and luster; Through adding oxidation inhibitor, improve the ability of the thermo oxidative aging of nylon 66 composition.
Above-mentioned nylon 66 composition can be widely used in industries such as automobile, machinery, electronics, electrical equipment, as making pipeline, film, electric fittings etc.The cylindrical shell of processing is tested by GB/T9647-2003 plastic pipe ring stiffness testing standard, and its rigidity obtains greatly to strengthen.Especially, adopt nano-TiO
2The film that ceramic powder and PA66 make; Method with GB15979-1995 is tested the bactericidal property of this mould material; Test shows material bactericidal range is wide, speed is fast, sterilizing rate is high, all reaches more than 90.00% to streptococcus aureus, Candida albicans, the intestinal bacteria sterilizing rate in 30min; The killing rate of hepatitis B virus in 20min reached 43.43%.
The above is merely embodiments of the invention; Be not so limit claim of the present invention; Every equivalent structure or equivalent flow process conversion that utilizes description of the present invention to do; Or directly or indirectly be used in other relevant technical fields, all in like manner be included in the scope of patent protection of the present invention.
Claims (10)
1. nylon 66 composition, its prescription is formed as follows:
PA66：50-80wt%；
Mineral filler: 10-40wt%;
Nano-ceramic powder: 10-20wt%;
Oxidation inhibitor: 0-1wt%;
Tinting pigment: 0-5wt%; And
Lubricating auxiliary agent: 0-0.5wt%.
2. nylon 66 composition according to claim 1 is characterized in that: said mineral filler comprises talcum powder, mica powder or kaolin, and granularity is at the 300-500 order.
3. nylon 66 composition according to claim 1 is characterized in that: said oxidation inhibitor comprises antioxidant CA, antioxidant 1010 or oxidation inhibitor 168.
4. nylon 66 composition according to claim 1 is characterized in that: the particle diameter of said nano-ceramic powder is in the 1-100 nanometer.
5. nylon 66 composition according to claim 1 is characterized in that: said nano-ceramic powder comprises nanometer ZrO
2Ceramic powder, nano-TiO
2Ceramic powder, nanometer AL
2O
3Ceramic powder, nanometer 3Y-TZP ceramic powder, nanometer PTCR ceramic powder or silicon-based nano ceramics powder.
6. nylon 66 composition according to claim 1 is characterized in that: said nano-ceramic powder comprises photocatalyst-type inorganic antibacterial material, metals ion burning type inorganic antibacterial material and rare-earth activated photochemical catalysis composite inorganic anti-biotic material.
7. nylon 66 composition according to claim 6 is characterized in that: have photocatalytic semiconductor material in the said photocatalyst-type inorganic antibacterial material, photocatalytic semiconductor material comprises TiO
2, ZrO
2, V
2O
3, ZnO, CdS, SeO
2, among the GaP, SiC one or more.
8. nylon 66 composition according to claim 6 is characterized in that: metals ion is a silver ions in the said metals ion burning type inorganic antibacterial material.
9. nylon 66 composition according to claim 1 is characterized in that: said lubricating auxiliary agent comprises calcium stearate or ethylene bis stearamide.
10. the preparation method of a nylon 66 composition may further comprise the steps:
1) takes by weighing material: PA66: 40-80wt%; Mineral filler: 10-40wt%; Nano-ceramic powder: 10-20wt%; Oxidation inhibitor: 0-1wt%; Tinting pigment: 0-5wt%; And lubricating auxiliary agent: 0-0.5wt%;
2) mixture: the above-mentioned material that takes by weighing is joined in the high-speed mixer, mix;
3) extruding pelletization or hot-forming.
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| CN201210227189.9A CN102732018B (en) | 2012-07-03 | 2012-07-03 | Nylon 66 composite and preparation method thereof |
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|---|---|---|---|
| CN201210227189.9A CN102732018B (en) | 2012-07-03 | 2012-07-03 | Nylon 66 composite and preparation method thereof |
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| CN102732018B CN102732018B (en) | 2015-02-25 |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103740099A (en) * | 2013-12-28 | 2014-04-23 | 重庆普利特新材料有限公司 | PA6 compound with stable colorability and preparation method thereof |
| CN104212165A (en) * | 2014-09-18 | 2014-12-17 | 常熟市沪虞塑料制品有限公司 | Aging-resistant environment-friendly plastic |
| CN106433102A (en) * | 2016-08-31 | 2017-02-22 | 浙江理工大学 | Preparation method of anti-aging polyamide film |
| CN106544751A (en) * | 2016-12-07 | 2017-03-29 | 怀宁县菲豹服饰有限公司 | A kind of deodorization and sterilization bamboo filament fibre, nylon66 fiber blending and modifying spinning fabric and preparation method thereof |
| CN107099134A (en) * | 2017-06-29 | 2017-08-29 | 苏州安特实业有限公司 | A kind of preparation method of the polyamide nano compound package material of high antibacterial |
| DE102016119531A1 (en) * | 2016-10-13 | 2018-04-19 | Lisa Dräxlmaier GmbH | Transition metal oxide stabilized zirconia in automotive plastics |
| CN112457665A (en) * | 2020-11-23 | 2021-03-09 | 山东广垠新材料有限公司 | Ceramic-like nylon material and preparation method thereof |
| CN113881221A (en) * | 2021-11-12 | 2022-01-04 | 惠州市晋裕塑料科技有限公司 | High-barrier nylon blending material |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1789335A (en) * | 2005-12-16 | 2006-06-21 | 攀钢集团攀枝花钢铁研究院 | Dedicated nano compound agglomerate for outdoors lamp and its preparation method |
-
2012
- 2012-07-03 CN CN201210227189.9A patent/CN102732018B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1789335A (en) * | 2005-12-16 | 2006-06-21 | 攀钢集团攀枝花钢铁研究院 | Dedicated nano compound agglomerate for outdoors lamp and its preparation method |
Non-Patent Citations (1)
| Title |
|---|
| 史琳琳 等: "纳米陶瓷的性能及其应用", 《2003 年纳微粉体制备与技术应用研讨会》, 1 September 2003 (2003-09-01) * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103740099A (en) * | 2013-12-28 | 2014-04-23 | 重庆普利特新材料有限公司 | PA6 compound with stable colorability and preparation method thereof |
| CN104212165A (en) * | 2014-09-18 | 2014-12-17 | 常熟市沪虞塑料制品有限公司 | Aging-resistant environment-friendly plastic |
| CN106433102A (en) * | 2016-08-31 | 2017-02-22 | 浙江理工大学 | Preparation method of anti-aging polyamide film |
| DE102016119531A1 (en) * | 2016-10-13 | 2018-04-19 | Lisa Dräxlmaier GmbH | Transition metal oxide stabilized zirconia in automotive plastics |
| DE102016119531B4 (en) * | 2016-10-13 | 2021-01-28 | Lisa Dräxlmaier GmbH | Molding compound comprising transition metal oxide stabilized zirconium dioxide as well as molded bodies, their production and use in the automotive sector |
| CN106544751A (en) * | 2016-12-07 | 2017-03-29 | 怀宁县菲豹服饰有限公司 | A kind of deodorization and sterilization bamboo filament fibre, nylon66 fiber blending and modifying spinning fabric and preparation method thereof |
| CN107099134A (en) * | 2017-06-29 | 2017-08-29 | 苏州安特实业有限公司 | A kind of preparation method of the polyamide nano compound package material of high antibacterial |
| CN112457665A (en) * | 2020-11-23 | 2021-03-09 | 山东广垠新材料有限公司 | Ceramic-like nylon material and preparation method thereof |
| CN113881221A (en) * | 2021-11-12 | 2022-01-04 | 惠州市晋裕塑料科技有限公司 | High-barrier nylon blending material |
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|---|---|
| CN102732018B (en) | 2015-02-25 |
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