CN105585843A - Low-precipitation red-phosphorus flame-retardant nylon material and preparation method and application thereof - Google Patents
Low-precipitation red-phosphorus flame-retardant nylon material and preparation method and application thereof Download PDFInfo
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- CN105585843A CN105585843A CN201610136916.9A CN201610136916A CN105585843A CN 105585843 A CN105585843 A CN 105585843A CN 201610136916 A CN201610136916 A CN 201610136916A CN 105585843 A CN105585843 A CN 105585843A
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- red phosphorus
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
The invention discloses a low-precipitation red-phosphorus flame-retardant nylon material and a preparation method and application thereof. The low-precipitation red-phosphorus flame-retardant nylon material is prepared from, by mass, 30%-80% of nylon resin, 5%-30% of red-phosphorus flame retardant, 0.1%-2% of red-phosphorus stabilizer, 0-10% of toughening agent, 10%-50% of reinforcing filler and 0.1%-5% of other additives. According to the low-precipitation red-phosphorus flame-retardant nylon material, the red-phosphorus flame retardant is adopted to be blended with other components, the red-phosphorus flame-retardant nylon material with good stability is prepared by adjusting the proportion of all the components, the red-phosphorus flame-retardant nylon material is low in phosphorus precipitation in a long-term high-temperature and high-humidity environment, and therefore corrosivity to metal and dies is reduced; meanwhile, the red-phosphorus flame-retardant nylon material has the good flame retardancy, electrical insulation property, mechanical property and molding liquidity.
Description
Technical field
The invention belongs to engineering plastic modification technical field, be specifically related to a kind of low red phosphorus flame-retardant nylon material of separating outMaterial and its preparation method and application.
Background technology
Red phosphorus combustion inhibitor is a kind of halogen-free flame retardants efficiently, is widely used in nylon fire proofing. Red phosphorus resistanceCombustion nylon material extensively should because having the advantages such as good anti-flammability, electrical insulation capability, mechanical mechanics propertyFor electronic enterprises.
But under the environment of long term high temperature or high humility, red phosphorus is easily oxidized and generates phosphoric acid and hydrogen phosphide. WaveThe hydrogen phosphide of sending out property has toxicity, harmful, and the phosphoric acid generating is separated out and is deposited on metal surface, holdsPerishable metal and mould, and reduced the CTI (ComparativeTrackingIndex) of moulding articlePerformance, and finally reduce service life of electric element, bring potential safety hazard.
In order to reduce separating out of red phosphorus, patent EP2072566 uses active carbon as absorbent, can effectively fallThe phosphorus of low red phosphorus is separated out the burst size with phosphine gas, but the CTI performance of material is very low. Patent US2635953 and US4698215 use the hydroxide of hydroxide aluminum and zinc or magnesium as red phosphorus stabilizing agent, butThe effect that inhibition phosphoric acid is separated out is also unsatisfactory. Because these metal hydroxides temperature tolerances are poor, extrudingEasy decomposes in process. Patent US4421728 uses titanium dioxide as red phosphorus stabilizing agent, butTitanium dioxide needs very high addition, could effectively reduce separating out of phosphoric acid, and significantly reduce red phosphorusThe mechanical mechanics property of Flame-retardant Glass Fiber Reinforced Pa material. Patent US4550133 uses carboxylic acid cadmium salt as redPhosphorus stabilizer agent, as adipic acid cadmium, cadmium oxalate etc., can well reduce that phosphorus is separated out content and phosphine gas is releasedHigh-volume. But carboxylic acid cadmium salt does not meet six environmental requirements of ROHS because containing cadmium element. Patent US20020127403 adopt silver powder and stannic hydroxide clad as red phosphorus stabilizing agent, can effectively prevent red phosphorusOxidized, the stability of increase red phosphorus, but cost is too expensive, and affect electrical insulation capability.
Summary of the invention
For solving the shortcoming and defect part of prior art, primary and foremost purpose of the present invention is to provide a kind of and is growingIn the environment of phase high temperature and high humidity, low-phosphorous stability red phosphorus flame-retardant nylon of separating out content, low metal protectionThe low red phosphorus flame-retardant nylon material of separating out of material. This material, in the environment of long term high temperature and high humidity, significantly reducesPhosphorus is separated out content and is reduced corrosion of metal, also has good anti-flammability, CTI performance, mechanics simultaneouslyPerformance.
Another object of the present invention is to provide the above-mentioned low preparation method who separates out red phosphorus flame-retardant nylon material.
A further object of the present invention is to provide above-mentioned low application of separating out red phosphorus flame-retardant nylon material.
The object of the invention is achieved through the following technical solutions:
A kind of low red phosphorus flame-retardant nylon material of separating out, composed of the following components by quality percentage composition:
Preferred, the described low red phosphorus flame-retardant nylon material of separating out is composed of the following components by quality percentage composition:
Described nylon resin is PA6, PA66, PA6/66, PA610, PA612, PA46, PA6T, PA9TOr one or both in PAMXD6.
Described red phosphorus combustion inhibitor is the red phosphorus master batch taking nylon as carrier.
Described red phosphorus stabilizing agent is light rare earth metal oxide, i.e. lanthanum (La), cerium in periodic table of elements III B family(Ce), in the metal oxide of praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu) elementAt least one.
Described flexibilizer is maleic anhydride graft POE (maleic anhydride stem grafting polyolefin elastomer), maleic acid(maleic anhydride connects for acid anhydride grafting EPDM (maleic anhydride graft ethylene propylene diene rubber) and maleic anhydride graft PPBranch polypropylene) at least one.
Described reinforcer be glass fibre, glass microballoon, carbon fiber, potassium titanate fibre, basalt fibre,In aramid fiber, wollastonite, calcium carbonate, mica, talcum powder, kaolin, calcium silicates and barium sulfate extremelyFew a kind of.
Described other additive is the mixture of antioxidant and lubricant. Wherein, antioxidant is preferably N, and N'-is two-(3-(3,5-di-tert-butyl-hydroxy phenyl) propiono) hexamethylene diamine, four [β-(3,5-di-t-butyl-4-hydroxy benzenesBase) propionic acid] at least one in pentaerythritol ester and three [2.4-di-tert-butyl-phenyl] phosphite ester, lubricant is excellentElect N as, N'-ethylene bis stearamide, calcium stearate, zinc stearate, pentaerythritol stearate, siliconeAt least one in lubricant and Tissuemat E.
The above-mentioned low red phosphorus flame-retardant nylon material preparation method that separates out, comprises the following steps: contain by mass percentageAmount takes raw material; Nylon resin, red phosphorus combustion inhibitor, red phosphorus stabilizing agent, flexibilizer, other additive are doneDry, then mix in the hopper that joins double screw extruder, by reinforcer from double screw extruderSide spout add, through melt blending extrude, cooling, air-dry, granulation, make the described low red phosphorus of separating outFire-retardant nylon material; Wherein, extruding processing temperature is 220-280 DEG C, screw speed 300-500 rev/min.
The low red phosphorus flame-retardant nylon material of separating out of the present invention can be suitable for manufacturing fiber, extrusion board and any classThe moulding article of type, also can be used for electronic and electric components, is especially operated in the electronics in high temperature wet environmentElectric component, as male component, low tension switch, connector, terminal, coil rack, breaker, relayDevice, electrical equipment base and support etc.
Compared with prior art, the present invention has the following advantages and beneficial effect:
The low red phosphorus flame-retardant nylon material of separating out of the present invention adopts red phosphorus stabilizing agent and other component mixtures, passes throughAdjust each component ratio, make the red phosphorus flame-retardant nylon material with good stability, it is high at long term high temperatureIn wet environment, there is the lower phosphorus property separated out, thereby reduce the corrosivity to metal and mould, also simultaneouslyThere is good anti-flammability, electrical insulation capability, mechanical property, moulding mobility.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limitIn this.
In the embodiment of the present invention and comparative example, use following component:
Nylon resin is nylon 66, and its intrinsic viscosity IV is 146ml/g, exists according to ISO307-2007 standardUnder 25 DEG C of conditions, test, use the EP158N purchased from Hua Feng.
Red phosphorus combustion inhibitor is the microencapsulation red phosphorus master batch of 50% content taking PA6 as carrier, uses purchased from sectionThe ExolitRP695 of Lay grace.
Red phosphorus stabilizing agent is anhydrous zinc borate, or magnesium hydroxide, or lanthana, or cerium oxide:
Anhydrous zinc borate, chemical molecular formula 2ZnO.3B2O3, use the ZB2300 (use that reaches chemical industry purchased from star shellfishIn comparative example).
Magnesium hydroxide, chemical molecular formula Mg (OH)2, use the YSM-5000 purchased from the mining industry of Yongxing, Dandong, grainFootpath D50=2 μ m (for comparative example).
Lanthana, chemical molecular formula La2O3, use the lanthana purchased from the logical prompt chemical industry in Zhengzhou, particle diameter D50＝4μm。
Cerium oxide, chemical molecular formula CeO2, use purchased from Guang Li new and high technology Materials Co., Ltd of Ganzhou CityCerium oxide, particle diameter D50=5 μ m.
Flexibilizer is maleic anhydride graft POE, uses the CMG9805 purchased from the liter of Nantong day.
Reinforcer is chopped glass fiber, uses the ECS301CL-3 purchased from Chongqing composite, fibre diameter10 μ m, the short length 4.5mm that cuts.
Other additives are the antioxidant 1098 (purchased from BASF) of 30% weight, the antioxidant of 30% weightThe lubricant stearic acid calcium of 168 (purchased from BASF) and 40% weight.
The concrete preparation method of embodiment and comparative example comprises the following steps: content takes former by mass percentageMaterial; Nylon resin, red phosphorus combustion inhibitor, red phosphorus stabilizing agent, flexibilizer, other additive are dried, thenMix in the hopper that joins double screw extruder the side feeding by reinforcer from double screw extruderMouthful add, through melt blending extrude, cooling, air-dry, granulation, make red phosphorus flame-retardant nylon material; ItsIn, double-screw extruder screw diameter is 40mm, and draw ratio is 40:1, and extruding processing temperature is 240-270 DEG C,Screw speed 350-450 rev/min.
The red phosphorus flame-retardant nylon material making is placed under 90 DEG C/12h of baking oven condition, fully dry. ThenBe injection molded into standard testing batten with injection machine, injection temperature is 80 DEG C of 270 DEG C, mould temperature.
Cantilever beam notched Izod impact strength testing standard is ASTMD256;
Melt index testing standard is ASTMD1238, and test condition is 275 DEG C/2.16kg;
Hot strength testing standard is ASTMD638;
Flame retardant test standard is UL94, and flame retardant rating is respectively HB, V2, V1, V0;
CTI (relative discharge tracking index) testing standard is IEC60112;
Test result CTI>=450V, is expressed as Pass, and CTI<450V is expressed as Failed;
Phosphorus is separated out method of testing:
Under the environmental condition of high temperature and high humility, carry out senile experiment, test phosphorus is separated out content. Test bars(80mm × 60mm × 3mm) is placed in 70 DEG C of water-baths, after 30 days and 60 days, (former by AASSub-absorption spectrometry) phosphide content in test water solution, show that phosphorus separates out content, with μ g phosphorus/g sampleMeter.
The low constituent (by quality percentage composition) of separating out red phosphorus flame-retardant nylon material comparative example and embodimentWith test result as shown in Table 1 and Table 2.
The data result of table 1 and table 2 shows, according to the present invention, adds lanthana, cerium oxide as red phosphorusStabilizing agent, has significantly reduced red phosphorus flame-retardant nylon material phosphorus under long term high temperature high humidity environment condition and has separated out content,Simultaneously red phosphorus flame-retardant nylon material of the present invention also have good anti-flammability, CTI performance and moulding mobility,Mechanical mechanics property.
Table 1 red phosphorus flame-retardant nylon material constituent mass percentage composition and the performance test results
Table 2 red phosphorus flame-retardant nylon material constituent mass percentage composition and the performance test results
Above-described embodiment is preferably embodiment of the present invention, but embodiments of the present invention are not subject to above-mentioned realityExecute routine restriction, other any do not deviate from the change done under Spirit Essence of the present invention and principle, modification,Substitute, combine, simplify, all should be equivalent substitute mode, within being included in protection scope of the present invention.
Claims (9)
1. the low red phosphorus flame-retardant nylon material of separating out, is characterized in that, the described low red phosphorus flame-retardant nylon of separating outMaterial is composed of the following components by quality percentage composition:
2. the low red phosphorus flame-retardant nylon material of separating out according to claim 1, is characterized in that, described lowSeparate out red phosphorus flame-retardant nylon material composed of the following components by quality percentage composition:
3. the low red phosphorus flame-retardant nylon material of separating out according to claim 1, is characterized in that described Buddhist nunDragon resin is PA6, PA66, PA6/66, PA610, PA612, PA46, PA6T, PA9T and PAMXD6In one or both.
4. the low red phosphorus flame-retardant nylon material of separating out according to claim 1, is characterized in that, described redPhosphorus fire retardant is the red phosphorus master batch taking nylon as carrier.
5. the low red phosphorus flame-retardant nylon material of separating out according to claim 1, is characterized in that, described redPhosphorus stabilizer agent is light rare earth metal oxide, be specially lanthanum in periodic table of elements III B family, cerium, praseodymium, neodymium, promethium,At least one in the metal oxide of samarium and europium element.
6. the low red phosphorus flame-retardant nylon material of separating out according to claim 1, is characterized in that described increasingTough dose be in maleic anhydride graft POE, maleic anhydride graft EPDM and maleic anhydride graft PP at leastA kind of.
7. the low red phosphorus flame-retardant nylon material of separating out according to claim 1, is characterized in that described increasingStrong filler be glass fibre, glass microballoon, carbon fiber, potassium titanate fibre, basalt fibre, aramid fiber,At least one in wollastonite, calcium carbonate, mica, talcum powder, kaolin, calcium silicates and barium sulfate; InstituteState the mixture that other additive is antioxidant and lubricant.
8. the low preparation method who separates out red phosphorus flame-retardant nylon material described in claim 1 to 7 any one, its spyLevy and be, comprise the following steps: content takes raw material by mass percentage; By nylon resin, red phosphorus flame-retardantAgent, red phosphorus stabilizing agent, flexibilizer, other additive are dried, and then mix and join twin-screw extrusionIn the hopper of machine, reinforcer is added from the side spout of double screw extruder, through melt blending extrude,Cooling, air-dry, granulation, make the described low red phosphorus flame-retardant nylon material of separating out; Wherein, extrude processing temperatureFor 220-280 DEG C, screw speed 300-500 rev/min.
Described in claim 1 to 7 any one the low red phosphorus flame-retardant nylon material of separating out at moulding article and electronicsApplication in electric component preparation.
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| CN201610136916.9A CN105585843A (en) | 2016-03-10 | 2016-03-10 | Low-precipitation red-phosphorus flame-retardant nylon material and preparation method and application thereof |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105907091A (en) * | 2016-06-01 | 2016-08-31 | 天津平高智能电气有限公司 | Insulating material for solid-sealed polar poles, solid-sealed polar pole and preparation method thereof |
| CN106531394A (en) * | 2016-12-17 | 2017-03-22 | 慈溪市凯澳塑料制品有限公司 | Electromagnetic coil, coil insulation skeleton and modified nylon material for preparing skeleton |
| CN106751778A (en) * | 2016-12-20 | 2017-05-31 | 浙江大学宁波理工学院 | Rare earth oxide and microcapsule red phosphorus cooperative flame retardant PA6 composites and preparation method thereof |
| CN107227020A (en) * | 2017-06-30 | 2017-10-03 | 徐州腾飞工程塑料有限公司 | It is a kind of for high-strength nylon material of vehicle and preparation method thereof |
| CN107254167A (en) * | 2017-06-09 | 2017-10-17 | 江苏特耐奇工程塑业有限公司 | Corrosion-resistant fire-retardant nylon material |
| CN109181291A (en) * | 2018-07-09 | 2019-01-11 | 中广核俊尔新材料有限公司 | A kind of blue red phosphorus flame-retardant reinforced polyamide material |
| CN109929244A (en) * | 2019-02-28 | 2019-06-25 | 株洲时代新材料科技股份有限公司 | A kind of red phosphorus flame-retardant nylon composite materials and preparation method thereof and the wherein measuring method of phosphorus amount of precipitation |
| CN112226078A (en) * | 2020-09-28 | 2021-01-15 | 天津金发新材料有限公司 | Nylon composite material and preparation method and application thereof |
| CN113527877A (en) * | 2020-04-14 | 2021-10-22 | 中蓝晨光化工研究设计院有限公司 | high-CTI-value black red phosphorus flame-retardant reinforced nylon 66 and preparation method thereof |
| CN113956655A (en) * | 2021-10-28 | 2022-01-21 | 上海欣洁商务服务有限公司 | Glass fiber reinforced flame-retardant PA66 material and preparation method thereof |
| WO2022110666A1 (en) * | 2020-11-25 | 2022-06-02 | 金发科技股份有限公司 | Red phosphorus flame-retardant polyamide composition, and preparation method therefor and application thereof |
| CN114672160A (en) * | 2022-03-17 | 2022-06-28 | 金发科技股份有限公司 | High-tracking-resistance red phosphorus flame-retardant polyamide composition and preparation method and application thereof |
| CN116656125A (en) * | 2023-05-19 | 2023-08-29 | 江苏金发科技新材料有限公司 | Nylon material and preparation method thereof |
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| CN101619166A (en) * | 2009-07-31 | 2010-01-06 | 金发科技股份有限公司 | Flame-retardant thermoplastic composite and preparation method thereof |
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Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105907091A (en) * | 2016-06-01 | 2016-08-31 | 天津平高智能电气有限公司 | Insulating material for solid-sealed polar poles, solid-sealed polar pole and preparation method thereof |
| CN106531394A (en) * | 2016-12-17 | 2017-03-22 | 慈溪市凯澳塑料制品有限公司 | Electromagnetic coil, coil insulation skeleton and modified nylon material for preparing skeleton |
| CN106751778B (en) * | 2016-12-20 | 2019-03-05 | 浙江大学宁波理工学院 | Rare earth oxide and microcapsule red phosphorus cooperative flame retardant PA6 composite material and preparation method |
| CN106751778A (en) * | 2016-12-20 | 2017-05-31 | 浙江大学宁波理工学院 | Rare earth oxide and microcapsule red phosphorus cooperative flame retardant PA6 composites and preparation method thereof |
| CN107254167A (en) * | 2017-06-09 | 2017-10-17 | 江苏特耐奇工程塑业有限公司 | Corrosion-resistant fire-retardant nylon material |
| CN107227020A (en) * | 2017-06-30 | 2017-10-03 | 徐州腾飞工程塑料有限公司 | It is a kind of for high-strength nylon material of vehicle and preparation method thereof |
| CN109181291B (en) * | 2018-07-09 | 2020-12-25 | 中广核俊尔新材料有限公司 | Blue red phosphorus flame-retardant reinforced polyamide material |
| CN109181291A (en) * | 2018-07-09 | 2019-01-11 | 中广核俊尔新材料有限公司 | A kind of blue red phosphorus flame-retardant reinforced polyamide material |
| CN109929244A (en) * | 2019-02-28 | 2019-06-25 | 株洲时代新材料科技股份有限公司 | A kind of red phosphorus flame-retardant nylon composite materials and preparation method thereof and the wherein measuring method of phosphorus amount of precipitation |
| CN109929244B (en) * | 2019-02-28 | 2021-08-17 | 株洲时代新材料科技股份有限公司 | Red phosphorus flame-retardant nylon composite material, preparation method thereof and method for measuring precipitation amount of phosphorus in composite material |
| CN113527877A (en) * | 2020-04-14 | 2021-10-22 | 中蓝晨光化工研究设计院有限公司 | high-CTI-value black red phosphorus flame-retardant reinforced nylon 66 and preparation method thereof |
| CN113527877B (en) * | 2020-04-14 | 2023-05-02 | 中蓝晨光化工研究设计院有限公司 | High CTI value black red phosphorus flame-retardant reinforced nylon 66 and preparation method thereof |
| CN112226078A (en) * | 2020-09-28 | 2021-01-15 | 天津金发新材料有限公司 | Nylon composite material and preparation method and application thereof |
| WO2022110666A1 (en) * | 2020-11-25 | 2022-06-02 | 金发科技股份有限公司 | Red phosphorus flame-retardant polyamide composition, and preparation method therefor and application thereof |
| CN113956655A (en) * | 2021-10-28 | 2022-01-21 | 上海欣洁商务服务有限公司 | Glass fiber reinforced flame-retardant PA66 material and preparation method thereof |
| CN113956655B (en) * | 2021-10-28 | 2022-06-10 | 上海欣洁商务服务有限公司 | Glass fiber reinforced flame-retardant PA66 material and preparation method thereof |
| CN114672160A (en) * | 2022-03-17 | 2022-06-28 | 金发科技股份有限公司 | High-tracking-resistance red phosphorus flame-retardant polyamide composition and preparation method and application thereof |
| CN114672160B (en) * | 2022-03-17 | 2023-11-21 | 金发科技股份有限公司 | Red phosphorus flame-retardant polyamide composition with high tracking resistance, and preparation method and application thereof |
| CN116656125A (en) * | 2023-05-19 | 2023-08-29 | 江苏金发科技新材料有限公司 | Nylon material and preparation method thereof |
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Address after: Conghua City Ao town Guangzhou city Guangdong province 510945 Longtan Jubao Industrial Zone Applicant after: GUANGZHOU SUPER-DRAGON ENGINEERING PLASTICS CO., LTD. Address before: Conghua City Ao town Guangzhou city Guangdong province 510945 Longtan Jubao Industrial Zone Applicant before: Guangzhou Super-Dragon Engineering plastic Co., Ltd. |
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Application publication date: 20160518 |