CN103013104B - Halogen-free filling flame-retardant nylon 6 composite material and preparation method thereof - Google Patents
Halogen-free filling flame-retardant nylon 6 composite material and preparation method thereof Download PDFInfo
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- CN103013104B CN103013104B CN201210576098.6A CN201210576098A CN103013104B CN 103013104 B CN103013104 B CN 103013104B CN 201210576098 A CN201210576098 A CN 201210576098A CN 103013104 B CN103013104 B CN 103013104B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/78—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling
- B29C48/875—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling for achieving a non-uniform temperature distribution, e.g. using barrels having both cooling and heating zones
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a halogen-free filling flame-retardant nylon 6 composite material and a preparation method thereof. The halogen-free filling flame-retardant nylon 6 composite material provided by the invention is characterized by being prepared from the following raw materials: 53-70 parts by weight of nylon 6 resin, 7-15 parts by weight of melamine cyanurate, 20-30 parts by weight of inorganic filling material, 0-5 parts by weight of synergistic flame retardant, and 1-5 parts by weight of processing agent. Compared with the prior art, the halogen-free filling flame-retardant nylon 6 composite material provided by the invention has the beneficial effects the halogen-free filling flame-retardant nylon 6 composite material is capable of passing the GWFI (Glow Wire Flammability Index) test at 960 DEG C, also has the characteristics of being low in cost, high in modulus and strength, excellent size stability, environment-friendly, flame-retardant and the like, and has good application prospect.
Description
Technical field
The present invention relates to the preparation method field of high molecular fire retardant material, particularly Halogen fills flame-retardant nylon 6 material and preparation method thereof.
Background technology
Along with the development of electronic enterprises, the demand of fire-retardant nylon material keeps increasing fast.Although halogen containing flame-retardant good flame retardation effect, during burning, the amount of being fuming is large, and produces toxic gas and cause secondary pollution.Melamine cyanurate, being called for short MCA, is a kind of nitrogenous compound that trimeric cyanamide and cyanuric acid are polymerized.As a kind of nitrogenated flame retardant, compared with halogenated flame retardant, toxicity is lower, has excellent flame-retardant comprehensive performance.Nylon 6 is that a kind of toughness is good, excellent electrical property, oil resistant, wear-resisting important engineering plastics, but when it is applied to electronic apparatus, transportation building field, also need to carry out fire-retardant finish.
" polymer material science and engineering " 20 (3) phases, Chinese patent 200510022046.4, Chinese patent 03135668.0 in 2004 discloses trimeric-cyanamide cyanurate fire-retardant nylon.But more than studying a kind of mode is that to carry out molecule to melamine cyanurate composite modified, and then prepare fire-retardant nylon, another kind of mode first prepares fire retardant in In-situ reaction mode.Chinese patent 200710011841.2 provides one and nylon 6, melamine cyanurate, oxidation inhibitor, triphenylphosphate or zinc borate is mixed, reactive extrursion method is adopted to prepare melamine cyanurate/nylon 6 fire retardant material, flame retardant properties can reach UL94V-0, but and the data such as unexposed GWFI test and mechanical property.
JP 60037829B2 describes a kind of flame-retardant polyamide composition, based on the weight of polymeric amide, comprise the melamine cyanurate of 3-30 % by weight and the mineral filler (such as talcum powder) of 5-60 % by weight, wherein the weight ratio of melamine cyanurate/mineral filler is adjusted between 1/5 and 1/3, illustrational composition all based on the weight of polymeric amide containing the melamine cyanurate (this corresponds to based on the mineral filler of the total amount 21.4wt% of composition and the melamine cyanurate of 7.1wt%) of the mineral filler of 30wt% and 10wt%.The shortcoming of this known daiamid composition is that the amount of filler is restricted.
Chinese patent application 200980126940.2, flame-retardant polyamide composition, disclose a kind of daiamid composition, said composition comprises polymeric amide, melamine cyanurate and the talcum as mineral filler, wherein the amount of talcum is higher than 25wt%, and the weight ratio of melamine cyanurate/talcum is higher than 1/3.When the talcous content for daiamid composition is 25%, increase the consumption of MAC, do not make the shortening of combustion time; When the amount of talcum used is more than 25%, the consumption increasing MAC to poly cyanamid cyanurate/talcum weight ratio higher than 1/3 time, can cause shortens combustion time, pass through smoothly the test of glowing filament 960 DEG C.Said composition is generally used for electrical and electronic parts industry, is mainly used in for miniature circuit breaker.
There is the problems such as non-environmental protection flame retardant, flame retardant rating is low, GWFI test is unstable in existing flame resistant filler nylon.Therefore, invent a kind of daiamid composition possessing the characteristics such as GWFI stable testing, environmental protection flame retardant, possess good application prospect at Low-voltage Electronic appliance field.
Summary of the invention
The object of this invention is to provide a kind of Halogen fire-retardant with Inorganic Fillers Filled, melamine cyanurate and synergistic fire retardant and fill fire-retardant Nylon 6 matrix material, be applicable to Low-voltage Electronic electric equipment products.Referring to acceptable combustion time of the present invention can smoothly by the GWFI test at 960 DEG C.
In order to achieve the above object, the invention provides a kind of Halogen and fill fire-retardant Nylon 6 matrix material, it is characterized in that, be made up of following raw material:
Nylon 6 53-70 weight part;
Melamine cyanurate 7-15 weight part;
Mineral filler 20-30 weight part;
Synergistic fire retardant 0-5 weight part;
Processing aid 1-5 weight part;
Described mineral filler is the one or more kinds of mixtures in talcum powder, wollastonite, globular glass microballon and flat glass fiber.
Described Nylon 6 is preferably low viscosity Nylon 6, is more preferably the Nylon 6 that relative viscosity is 2.2-2.5.
Preferably, described talcous median size is 1000-5000 order; The length-to-diameter ratio of described wollastonite is 10-20: 1; The diameter of described globular glass microballon is 10-30 μm; It is 2-6 that described flat glass fiber is preferably main cross section axle with the dimensional ratios of time cross section axis, and to be that 2-3mm is short cut flat glass fiber to length.
Described synergistic fire retardant is preferably the one or more kinds of mixtures in zinc borate, phosphonium flame retardant and polynite.
More preferably, described phosphonium flame retardant is one in phenoxy phosphazene compound and triphenylphosphate or its mixture.Described polynite is the sodium-based montmorillonite that average wafer thickness is less than 25nm.
Described processing aid is preferably at least one in lubricant, oxidation inhibitor, stablizer and releasing agent.
More preferably, described lubricant is one or more the composition in fatty acid ester blends, white mineral oil and pentaerythritol stearate; Described oxidation inhibitor is one in Hinered phenols antioxidant and phosphite ester kind antioxidant or its composition; Described releasing agent is stearate; Described stablizer is aromatic amine stablizer.
Further; described Hinered phenols antioxidant is four (methylene radical-3-(3; 5-di-tert-butyl-hydroxy phenyl) propionic ester) methane, N; N '-bis-[3-(3; 5-di-tert-butyl-hydroxy phenyl) propionyl) hexanediamine, triglycol two-3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester, β-(4-hydroxyl-3; 5-di-tert-butyl-phenyl) the positive octadecanol ester of propionic acid or N; N '-bis-[3-(3,5-di-tert-butyl-hydroxy phenyl) propionyl] hydrazine.
Further, described phosphite antioxidant is three (2,4-di-tert-butyl-phenyl) phosphorous acid ester, two (2.4-di-tert-butyl-phenyl) pentaerythritol diphosphites, four (2,4-di-tert-butylphenol)-4,4 '-xenyl diphosphites or two (2,6-di-tert-butyl-phenyl) pentaerythritol diphosphites or triphenyl phosphite.
Present invention also offers the preparation method that above-mentioned Halogen fills fire-retardant Nylon 6 matrix material, it is characterized in that, concrete steps are:
The first step: Nylon 6 53-70 weight part, melamine cyanurate 7-15 weight part, mineral filler 20-30 weight part, synergistic fire retardant 0-5 weight part and processing aid 1-5 weight part are added high mixer and is mixed to get Preblend;
Second step: the Preblend the first step obtained joins twin screw extruder from the main spout of twin screw extruder, carries out melt extruding, cooling granulation, obtains Halogen and fills fire-retardant Nylon 6 matrix material, wherein, the processing parameter of twin screw extruder is: district's temperature 210 DEG C, two district's temperature 230 DEG C, three district's temperature 250 DEG C, four district's temperature 250 DEG C, five district's temperature 240 DEG C, six district's temperature 240 DEG C, seven district's temperature 240 DEG C, eight district's temperature 230 DEG C, nine district's temperature 240 DEG C; Engine speed 350 revs/min.
Halogen of the present invention fills fire-retardant Nylon 6 matrix material mainly for the manufacture of low-voltage apparatus goods.
Compared with prior art, the invention has the beneficial effects as follows:
Halogen of the present invention is filled fire-retardant Nylon 6 matrix material and by the GWFI test at 960 DEG C, also can be possessed the characteristics such as the dimensional stability of low cost, high-modulus, high strength and excellence, environmental protection flame retardant, possess good application prospect.
Compared with background technology " polymer material science and engineering " 20 (3) phases in 2004, Chinese patent 200510022046.4, Chinese patent 03135668.0, it is composite modified that the present invention does not carry out molecule to melamine cyanurate, then prepares fire-retardant nylon; Neither first prepare fire retardant at modification of nylon in In-situ reaction mode, but directly with melamine cyanurate through melt extruding modification of nylon, preparation technology of the present invention is more simple by contrast, Production Flow Chart and the cycle short, cost-saving.Compare with Chinese patent application 200980126940.2 with Chinese patent 200710011841.2, JP 60037829B2, the present invention keeps material excellent mechanical performances by adding mineral filler (comprising talcum powder, wollastonite, glass microballon, flat glass) while the flame retardant properties improving material, and this is because the enhancement that is added with of these mineral fillers improves the performances such as the modulus of material; Be on the other hand, during burning in the expansion process of carburization zone, mineral filler can well combine with carburization zone, be conducive to the formation of finer and close carburization zone or can effectively strengthen resin matrix and carburization zone, so just can strengthen flame retardant properties as a part for carburization zone, so just significantly improve flame retardant resistance.Simultaneously synergistic fire retardant selection and with filler with the use of Flame Retardancy can and mechanical property raising in serve very crucial effect.
Embodiment
For making the present invention become apparent, hereby with preferred embodiment, be described in detail below.
Embodiment 1-11
In the raw material that embodiment 1-11 adopts, nylon 6 is PA6M2400 (newly meeting U.S.A reaches production); Melamine cyanurate is commercially available powder (production of Sichuan fine chemistry industry); Talcum powder is 3000 object superfine talcum powders; Wollastonite is length-to-diameter ratio is 15-20: 1 needle-like wollastonite; The mean diameter of globular glass microballon is about 15 μm; Flat glass fiber is main cross section axle is 2 with the dimensional ratios of time cross section axis, and length is the chopped strand of 2-3mm.Polynite is the sodium-based montmorillonite DK5 of Zhejiang Feng Hong clay Chemical Manufacture; Zinc borate is the ZB-2335 of Zibo rising sun shellfish Chemical Manufacture; Phenoxy group polyphosphonitrile is the KP-735NA of Zibo indigo plant print Chemical Manufacture; Triphenylphosphate is Changzhou section peace Chemical Manufacture; Stablizer is polycarbodiimide, adopts the STABAXOL-1 of TUV chemical production; Oxidation inhibitor is N, N '-bis--(3-(3,5-di-tert-butyl-hydroxy phenyl) propionyl) hexanediamine (Irganox 1098 of Ciba company) and three [2.4-di-tert-butyl-phenyl] phosphorous acid ester (Irganox 168 of Ciba company); Lubricant is the TR044 of Struktol company of the U.S.; Releasing agent is calcium stearate.
In embodiment 1-11 and comparative example, the weight of each raw material is according to shown in table 1, and its preparation method is as follows:
(1) according to each material content (weight part), each raw material is added high mixer and be mixed to get Preblend;
(2) Preblend is joined twin screw extruder from the main spout of twin screw extruder, carries out melt extruding, cooling granulation, obtain Halogen and fill fire-retardant Nylon 6 matrix material, wherein, the processing parameter of twin screw extruder is: district's temperature 210 DEG C, two district's temperature 230 DEG C, three district's temperature 250 DEG C, four district's temperature 250 DEG C, five district's temperature 240 DEG C, six district's temperature 240 DEG C, seven district's temperature 240 DEG C, eight district's temperature 230 DEG C, nine district's temperature 240 DEG C; Engine speed 350 revs/min.
Method for testing performance of the present invention and standard are:
Tensile strength is tested according to ISO527-2 standard; Flexural strength and modulus in flexure are tested according to ISO178 standard; Notched Izod impact strength is tested according to ISO179 standard; Fire-retardant GWFI test is according to IEC60695 standard testing, and each test result is as shown in table 1.
As can be seen from Table 1, Halogen prepared in accordance with the present invention is filled fire-retardant Nylon 6 matrix material and is not only had good mechanical property, and there is excellent flame retardant properties, can be widely used in Low-voltage Electronic electrical equipment, etc. require fully to meet GWFI test request in higher field to material mechanical performance and flame retardant properties.The present invention passes through the flame-retardant nylon 6 material of MCA or MCA and synergistic fire retardant, can smoothly by 960 DEG C, the GWFI testing level of 1mm, during burning, low cigarette, low toxicity, material monolithic keeps good mechanical property, especially the modulus of material significantly improves simultaneously, and the good fluidity of system, be beneficial to process for processing.Compared with other flame-retardant nylon 6 materials, fire retardant material of the present invention is the fire retardant material of efficient halogen-free environmental protection, can fully meet low-voltage apparatus service requirements.
Claims (6)
1. Halogen fills a fire-retardant Nylon 6 matrix material, it is characterized in that, is made up of following raw material:
Nylon 6 53-70 weight part;
Melamine cyanurate 7-15 weight part;
Mineral filler 20-30 weight part;
Synergistic fire retardant 3-5 weight part;
Processing aid 1-5 weight part;
Described mineral filler is flat glass fiber; Described synergistic fire retardant is the one or more kinds of mixtures in zinc borate, phosphonium flame retardant and polynite.
2. Halogen as claimed in claim 1 fills fire-retardant Nylon 6 matrix material, it is characterized in that, the Nylon 6 of described Nylon 6 to be relative viscosity be 2.2-2.5.
3. Halogen as claimed in claim 1 fills fire-retardant Nylon 6 matrix material, it is characterized in that, described phosphonium flame retardant is one in phenoxy phosphazene compound and triphenylphosphate or its mixture.
4. Halogen as claimed in claim 1 fills fire-retardant Nylon 6 matrix material, and it is characterized in that, described processing aid is at least one in lubricant, oxidation inhibitor, stablizer and releasing agent.
5. Halogen as claimed in claim 4 fills fire-retardant Nylon 6 matrix material, and it is characterized in that, described lubricant is one or more the composition in fatty acid ester blends, white mineral oil and pentaerythritol stearate; Described oxidation inhibitor is one in Hinered phenols antioxidant and phosphite ester kind antioxidant or its composition; Described releasing agent is stearate; Described stablizer is aromatic amine stablizer.
6. Halogen according to claim 1 fills the preparation method of fire-retardant Nylon 6 matrix material, and it is characterized in that, concrete steps are:
The first step: Nylon 6 53-70 weight part, melamine cyanurate 7-15 weight part, mineral filler 20-30 weight part, synergistic fire retardant 0-5 weight part and processing aid 1-5 weight part are added high mixer and is mixed to get Preblend;
Second step: the Preblend the first step obtained joins twin screw extruder from the main spout of twin screw extruder, carries out melt extruding, cooling granulation, obtains Halogen and fills fire-retardant Nylon 6 matrix material, wherein, the processing parameter of twin screw extruder is: district's temperature 210 DEG C, two district's temperature 230 DEG C, three district's temperature 250 DEG C, four district's temperature 250 DEG C, five district's temperature 240 DEG C, six district's temperature 240 DEG C, seven district's temperature 240 DEG C, eight district's temperature 230 DEG C, nine district's temperature 240 DEG C; Engine speed 350 revs/min.
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| CN201210576098.6A CN103013104B (en) | 2012-12-26 | 2012-12-26 | Halogen-free filling flame-retardant nylon 6 composite material and preparation method thereof |
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| CN201210576098.6A CN103013104B (en) | 2012-12-26 | 2012-12-26 | Halogen-free filling flame-retardant nylon 6 composite material and preparation method thereof |
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| EP2924068A1 (en) | 2014-03-26 | 2015-09-30 | LANXESS Deutschland GmbH | Polyamide compositions |
| EP2924065A1 (en) | 2014-03-26 | 2015-09-30 | LANXESS Deutschland GmbH | Polyamide compositions |
| EP2924067A1 (en) * | 2014-03-26 | 2015-09-30 | LANXESS Deutschland GmbH | Polyamide compositions |
| CN103910999A (en) * | 2014-04-02 | 2014-07-09 | 合肥杰事杰新材料股份有限公司 | High-glowing nylon 6 composition and preparation method thereof |
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| DE202014008607U1 (en) | 2014-10-31 | 2014-11-24 | Lanxess Deutschland Gmbh | polyamide compositions |
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