CN103627168B - A kind of Special halogen-free flame-retardant master batch for nylon and preparation method thereof - Google Patents
A kind of Special halogen-free flame-retardant master batch for nylon and preparation method thereof Download PDFInfo
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- CN103627168B CN103627168B CN201310571215.4A CN201310571215A CN103627168B CN 103627168 B CN103627168 B CN 103627168B CN 201310571215 A CN201310571215 A CN 201310571215A CN 103627168 B CN103627168 B CN 103627168B
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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
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
- B29B9/065—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion under-water, e.g. underwater pelletizers
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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
- B29C48/92—Measuring, controlling or regulating
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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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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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
- C08L2201/22—Halogen free composition
Abstract
The invention discloses a kind of Special halogen-free flame-retardant master batch for nylon, be made up of the following raw material measured by weight percentage: PA6 resin 20 ~ 48%, nitrogenated flame retardant 50 ~ 70%, primary antioxidant 0.4 ~ 2.0%, auxiliary antioxidant 0.6 ~ 3.0%, external lubricant 0.8 ~ 3.0% and internal lubricant 0.2 ~ 2.0%.The invention solves the blanking difficulty that adopts MCA fire retardant to prepare to cause due to MCA fire retardant self-characteristic in fire-retardant nylon material process or the uneven problem of feeding, this master batch has good distribution ability simultaneously, good flame-retardance energy, asepsis environment-protecting, the feature such as safe and reliable and easy to use.The invention also discloses a kind of preparation method of Special halogen-free flame-retardant master batch for nylon, the method adopts the preparation of vertical cut formula underwater cutpellet technique, high-concentration flame-retardant masterbatch is achieved, the usage quantity of master batch in following process process can be reduced, weaken the impact of carrier in concrete material.
Description
Technical field
The present invention relates to the flame-retardant modified field of macromolecular material, particularly relate to a kind of high density Special halogen-free flame-retardant master batch for nylon, the invention still further relates to a kind of preparation method of high density Special halogen-free flame-retardant master batch for nylon.
Background technology
Nylon is a kind of excellent property, of many uses, the engineering plastics of large usage quantity, has the features such as excellent mechanical property, wear resistance, good processing characteristics and chemical reagent resistance, is widely used in the fields such as automobile, electrical equipment, communication, electronics and machinery.Along with the high speed development of society, the requirement of such enterprise to nylon product performance is also more and more higher, and unmodified nylon plastic flame retardant resistance is poor, only can reach V-2 or the HB rank according to UL94 vertical combustion testing standard, cannot satisfy the demands of consumers far away.
Melamine cyanurate (MCA) is a kind of nitrogen system bittern-free fire retardant of excellent property, compared with phosphorous, halogen-containing flame retardant, MCA fire retardant has the advantages such as toxicity is low, heat resistance is high, Heat stability is good, flame retarding efficiency are high, suitability is strong, low price, be particularly useful for the flame-retardant modified of the nylon material not adding filling, according to different types of nylon kind, the MCA fire retardant adding 6 ~ 14% can reach V-0 level.The fire-retardant nylon goods using MCA fire retardant to prepare, have do not fade, feature that non-blooming, electrical property and mechanical property etc. are excellent.
But traditional MCA fire retardant is generally particle diameter is the powder of 2 ~ 25 μm, its molecule has certain polarity, and loose porous between powder particles, surface energy is high, makes the MCA fire retardant very easily moisture absorption and caking, in the preparation process of nylon material, MCA fire retardant is easily adsorbed on feed hopper wall, thus cause blanking difficulty, the problem such as feeding is uneven, and to change the line of production or in stopping production process, equipment is difficult to cleaning, and dust pollution is serious.In addition, because the particle diameter of MCA powder is less, in processing units, be difficult to dispersion, fire retardant practical efficiency is low, and the flame retardant resistance of prepared nylon material is declined.
Summary of the invention
The object of the invention is to propose a kind of Special halogen-free flame-retardant master batch for nylon, this nylon halogen-free flame retardant master batch solves the problem that blanking is difficult or feeding is uneven that nylon material causes due to MCA fire retardant self-characteristic in preparation process, and this master batch has good distribution ability, good flame-retardance energy, asepsis environment-protecting, the feature such as safe and reliable and easy to use.
In order to solve prior art problem, the present invention is achieved through the following technical solutions:
A kind of Special halogen-free flame-retardant master batch for nylon, is made up of the following raw material measured by weight percentage: PA6 resin 20 ~ 48%, nitrogenated flame retardant 50 ~ 70%, primary antioxidant 0.4 ~ 2.0%, auxiliary antioxidant 0.6 ~ 3.0%, external lubricant 0.8 ~ 3.0% and internal lubricant 0.2 ~ 2.0%.
The relative viscosity of described PA6 resin is 1.7 ~ 2.8.
Described nitrogenated flame retardant is MCA fire retardant.
Described MCA fire retardant is through dry powder prilling, and the particle diameter of MCA fire retardant is 0.1 ~ 4mm.
Described primary antioxidant is the combination of any one or several in oxidation inhibitor 1098, antioxidant 1010 and oxidation inhibitor 1024.
Described auxiliary antioxidant is the combination of any one or several in oxidation inhibitor 412S, irgasfos 168, anti-oxidant DLTP and oxidation inhibitor DSTP.
Described external lubricant is the combination of any one or several in silicone based lubricant, calcium stearate and Zinic stearas.
Described internal lubricant is the combination of any one or several in polyamide wax, montanin wax, EBS and TAF.
Another object of the present invention is to the preparation method proposing a kind of Special halogen-free flame-retardant master batch for nylon, comprise the following steps:
1) by PA6 resin dry 6 ~ 12h at the temperature of 90 ~ 100 DEG C, to the water content of PA6 resin lower than 0.1%;
2) by nitrogenated flame retardant dry 4 ~ 8h at the temperature of 110 ~ 120 DEG C, to the water content of nitrogenated flame retardant lower than 0.05%;
3) take the raw material of formula ratio, other raw materials outside removing fire retardant are mixed, and stirs;
4) added in parallel dual-screw extruding machine by the raw material after mixing through step 3) and carry out melt blending and extrude, in the feeding of side, add nitrogenated flame retardant, the temperature in each district of parallel dual-screw extruding machine controls between 230 ~ 240 DEG C simultaneously;
5) use direct cutting type underwater granule cutter to carry out pelletizing to the material after step 4, after cooling, dehydration, oven dry, sieving technology, obtain Special halogen-free flame-retardant master batch for nylon.
The invention solves the blanking difficulty that adopts MCA fire retardant to prepare to cause due to MCA fire retardant self-characteristic in fire-retardant nylon material process or the uneven problem of feeding.The master batch of gained of the present invention has pre-dispersed effect, MCA fire retardant can better disperse in nylon material, the flame retarding efficiency of fire retardant can be improved, thus reduce the usage quantity of fire retardant, in actual application, this master batch can directly and nylon material blended after carry out injection molding process or extruding-out process, even very weak injection moulding machine, single screw extrusion machine or the counter rotation twin screw extruder of dispersive ability also can obtain gratifying dispersion effect.The features such as master batch of the present invention also has good distribution ability, good flame-retardance energy, asepsis environment-protecting, safe and reliable and easy to use.
In addition, the present invention adopts advanced vertical cut formula underwater cutpellet technique preparation, high-concentration flame-retardant masterbatch is achieved, can reduces the usage quantity of master batch in following process process, weaken the impact of carrier in concrete material.
Embodiment
Present invention is disclosed a kind of Special halogen-free flame-retardant master batch for nylon, be made up of the following raw material measured by weight percentage: PA6 resin 20 ~ 48%, nitrogenated flame retardant 50 ~ 70%, primary antioxidant 0.4 ~ 2.0%, auxiliary antioxidant 0.6 ~ 3.0%, external lubricant 0.8 ~ 3.0% and internal lubricant 0.2 ~ 2.0%.
The relative viscosity of PA6 resin of the present invention is 1.7 ~ 2.8.The PA6 resin of relative viscosity between 1.7 ~ 2.8 all can be used as the present invention's nylon resin, the trade mark specifically produced as dutch royal DSM group is the PA6 resin of 1010C2, and the trade mark that and for example Meida Nylon Co., Ltd., Xinhui, Guangdong produces is PA6 resin of M2400 etc.
In the present invention, nitrogenated flame retardant is MCA fire retardant, and MCA fire retardant is through dry powder prilling, and the particle diameter of MCA fire retardant is 0.1 ~ 4mm.As one of the present invention preferred embodiment, the trade mark of MCA fire retardant is MCA-12, and the MCA fire retardant of this trade mark is through dry powder prilling, and particle diameter is 0.1 ~ 4mm.
In the present invention, oxidation inhibitor is combined by primary antioxidant and auxiliary antioxidant and obtains, primary antioxidant is the combination of any one or several in oxidation inhibitor 1098, antioxidant 1010 and oxidation inhibitor 1024, and auxiliary antioxidant is the combination of any one or several in oxidation inhibitor 412S, irgasfos 168, anti-oxidant DLTP and oxidation inhibitor DSTP.With master batch 100 weight part be total deal metering, the weight part of primary antioxidant is 0.4 ~ 2.0, and the weight part of auxiliary antioxidant is 0.6 ~ 3.0.As one of the present invention preferred embodiment, the preferred oxidation inhibitor 1098 of primary antioxidant, the preferred irgasfos 168 of auxiliary antioxidant.
In the present invention, lubricant is obtained by external lubricant and interior lubricating combination, external lubricant is the combination of any one or several in silicone based lubricant, calcium stearate and Zinic stearas, and internal lubricant is the combination of any one or several in polyamide wax, montanin wax, EBS and TAF.With master batch 100 weight part be total deal metering, the weight part of external lubricant is 0.8 ~ 3.0, and the weight part of internal lubricant is 0.2 ~ 2.0.As one of the present invention preferred embodiment, the preferred silicone powder of external lubricant, the trade mark being selected from the production of Degussa (Germany) chemical inc is the silicone powder of E525, the preferred C wax of internal lubricant, and the trade mark being selected from the production of German Clariant chemical company is the C wax of LicowaxC.
Another object of the present invention is to the preparation method proposing a kind of Special halogen-free flame-retardant master batch for nylon, comprise the following steps:
1) by PA6 resin dry 6 ~ 12h at the temperature of 90 ~ 100 DEG C, to the water content of PA6 resin lower than 0.1%;
2) by nitrogenated flame retardant dry 4 ~ 8h at the temperature of 110 ~ 120 DEG C, to the water content of nitrogenated flame retardant lower than 0.05%;
3) take the raw material of formula ratio, other raw materials outside removing fire retardant are mixed, and stirs;
4) raw material after mixing through step 3) is added in parallel dual-screw extruding machine carry out melt blending and extrude, in the feeding of side, add nitrogenated flame retardant simultaneously, wherein, the quality of material of main feeding and the feeding of side feeding unit time is than being 2:(3 ~ 5), parallel dual-screw extruding machine each district temperature controls between 230 ~ 240 DEG C;
5) direct cutting type underwater granule cutter is used to carry out pelletizing to the material after step 4; after cooling, dehydration, oven dry, sieving technology; obtain the special halogen-free flame-retardant master batch of dragon of water ratio≤0.2%, adopt the packing of aluminium foil moisture-proof packing bag or directly carry out the production that lower one technique carries out nylon material.
In order to the understanding of those skilled in the art, below by way of specific embodiment, further detailed description is done to the present invention.It should be noted that, in following examples, each raw material all can be replaced by other raw materials disclosed in this invention, because its performance is similar, therefore does not repeat one by one.
Embodiment 1
A preparation method for Special halogen-free flame-retardant master batch for nylon, comprises the following steps:
1) by PA6 resin (M2400) dry 6 ~ 12h at the temperature of 90 ~ 100 DEG C, to the water content of PA6 resin (M2400) lower than 0.1%;
2) by MCA-12 fire retardant dry 4 ~ 8h at the temperature of 110 ~ 120 DEG C, to the water content of MCA-12 fire retardant lower than 0.05%;
3) raw material PA6 resin (M2400) 46%, MCA-12 fire retardant 50%, oxidation inhibitor 10981.4%, irgasfos 168 1.6%, silicone powder E5250.8% and internal lubricant LicowaxC0.2% is taken by weight percentage, other raw materials outside removing MCA-12 fire retardant are mixed, and stirs;
4) raw material after mixing through step 3) is added in parallel dual-screw extruding machine carry out melt blending and extrude, in the feeding of side, add MCA-12 fire retardant simultaneously, wherein, the feeding quality of material of main feeding and side feeding unit time is than being 2:(3 ~ 5), the temperature in each district of parallel dual-screw extruding machine controls between 230 ~ 240 DEG C;
5) direct cutting type underwater granule cutter is used to carry out pelletizing to the material after step 4); temperature≤40 DEG C of recirculated water; after cooling, dehydration, oven dry, sieving technology; obtain water ratio≤0.2% of Special halogen-free flame-retardant master batch for nylon master batch, adopt aluminium foil weather-proof dressing by the packing of net weight 25kg/ bag or directly carry out the production that lower one technique carries out nylon material.
Embodiment 2
A preparation method for Special halogen-free flame-retardant master batch for nylon, comprises the following steps:
1) by PA6 resin (M2400) dry 6 ~ 12h at the temperature of 90 ~ 100 DEG C, to the water content of PA6 resin (M2400) lower than 0.1%;
2) by MCA-12 fire retardant dry 4 ~ 8h at the temperature of 110 ~ 120 DEG C, to the water content of MCA-12 fire retardant lower than 0.05%;
3) raw material PA6 resin (M2400) 37%, MCA-12 fire retardant 60%, oxidation inhibitor 10980.4%, irgasfos 168 0.6%, silicone powder E5251.0% and internal lubricant LicowaxC1.0% is taken by weight percentage, other raw materials outside removing MCA-12 fire retardant are mixed, and stirs;
4) raw material after mixing through step 3) is added in parallel dual-screw extruding machine carry out melt blending and extrude, in the feeding of side, add MCA-12 fire retardant simultaneously, wherein, the feeding quality of material of main feeding and side feeding unit time is than being 2:(3 ~ 5), the temperature in each district of parallel dual-screw extruding machine controls between 230 ~ 240 DEG C;
5) direct cutting type underwater granule cutter is used to carry out pelletizing to the material after step 4); temperature≤40 DEG C of recirculated water; after cooling, dehydration, oven dry, sieving technology; obtain water ratio≤0.2% of Special halogen-free flame-retardant master batch for nylon master batch, adopt aluminium foil weather-proof dressing by the packing of net weight 25kg/ bag or directly carry out the production that lower one technique carries out nylon material.
Embodiment 3
A preparation method for Special halogen-free flame-retardant master batch for nylon, comprises the following steps:
1) by PA6 resin (1010C2) dry 6 ~ 12h at the temperature of 90 ~ 100 DEG C, to the water content of PA6 resin (1010C2) lower than 0.1%;
2) by MCA-12 fire retardant dry 4 ~ 8h at the temperature of 110 ~ 120 DEG C, to the water content of MCA-12 fire retardant lower than 0.05%;
3) raw material PA6 resin (1010C2) 27%, MCA-12 fire retardant 70%, oxidation inhibitor 10980.4%, irgasfos 168 0.6%, silicone powder E5251.0% and internal lubricant LicowaxC1.0% is taken by weight percentage, other raw materials outside removing MCA-12 fire retardant are mixed, and stirs;
4) raw material after mixing through step 3) is added in parallel dual-screw extruding machine carry out melt blending and extrude, in the feeding of side, add MCA-12 fire retardant simultaneously, wherein, the feeding quality of material of main feeding and side feeding unit time is than being 2:(3 ~ 5), the temperature in each district of parallel dual-screw extruding machine controls between 230 ~ 240 DEG C;
5) direct cutting type underwater granule cutter is used to carry out pelletizing to the material after step 4); temperature≤40 DEG C of recirculated water; after cooling, dehydration, oven dry, sieving technology; obtain water ratio≤0.2% of Special halogen-free flame-retardant master batch for nylon master batch, adopt aluminium foil weather-proof dressing by the packing of net weight 25kg/ bag or directly carry out the production that lower one technique carries out nylon material.
Embodiment 4
A preparation method for Special halogen-free flame-retardant master batch for nylon, comprises the following steps:
1) by PA6 resin (1010C2) dry 6 ~ 12h at the temperature of 90 ~ 100 DEG C, to the water content of PA6 resin (1010C2) lower than 0.1%;
2) by MCA-12 fire retardant dry 4 ~ 8h at the temperature of 110 ~ 120 DEG C, to the water content of MCA-12 fire retardant lower than 0.05%;
3) raw material PA6 resin (1010C2) 20%, MCA-12 fire retardant 70%, oxidation inhibitor 10982.0%, irgasfos 168 3.0%, silicone powder E5253.0% and internal lubricant LicowaxC2.0% is taken by weight percentage, other raw materials outside removing MCA-12 fire retardant are mixed, and stirs;
4) raw material after mixing through step 3) is added in parallel dual-screw extruding machine carry out melt blending and extrude, in the feeding of side, add MCA-12 fire retardant simultaneously, wherein, the feeding quality of material of main feeding and side feeding unit time is than being 2:(3 ~ 5), the temperature in each district of parallel dual-screw extruding machine controls between 230 ~ 240 DEG C;
5) direct cutting type underwater granule cutter is used to carry out pelletizing to the material after step 4); temperature≤40 DEG C of recirculated water; after cooling, dehydration, oven dry, sieving technology; obtain water ratio≤0.2% of Special halogen-free flame-retardant master batch for nylon master batch, adopt aluminium foil weather-proof dressing by the packing of net weight 25kg/ bag or directly carry out the production that lower one technique carries out nylon material.
In above-described embodiment 1 ~ 4, the technical indicator of gained master batch is as shown in table 1:
| Technical indicator | Unit | Testing method | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Outward appearance | --- | --- | Dry and comfortable, bright and clean, closely knit, color is real white | Dry and comfortable, bright and clean, closely knit, color is real white | Dry and comfortable, bright and clean, closely knit, color is real white | Dry and comfortable, bright and clean, closely knit, color is real white |
| Density | g/cm 3 | ASTM D792 | 1.35 | 1.38 | 1.40 | 1.41 |
| Fugitive constituent | % | ASTM D1416 | 0.09 | 0.10 | 0.10 | 0.11 |
| Ash | % | GB/T 9345 | 0.15 | 0.15 | 0.17 | 0.16 |
Table 1
Master batch 16%(weight ratio by gained in above-described embodiment 1 ~ 4) with the PA66 resin 84%(weight ratio of relative viscosity 2.7) blended, directly carry out the test bars that injection moulding obtains standard, injection temperature is 245 ~ 260 DEG C, wherein, in the preparation process of nylon material, according to the difference of nylon resin kind, the temperature in injection molding process is generally 230 ~ 270 DEG C.Shown in the performance test results table 2 of nylon material:
| Performance | Unit | Testing method | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Density | g/cm 3 | ASTM D792 | 1.16 | 1.17 | 1.18 | 1.18 |
| Melt flow rate (MFR)/275 DEG C, 0.325kg | g/10min | ASTM D1238 | 10.2 | 8.9 | 7.8 | 7.3 |
| Heat-drawn wire/1.82MPa | ℃ | ASTM D648 | 101 | 103 | 105 | 104 |
| Tensile strength/23 DEG C | MPa | ASTM D638 | 80 | 82 | 78 | 83 |
| Flexural strength/23 DEG C | MPa | ASTM D790 | 102 | 101 | 105 | 106 |
| Modulus in flexure/23 DEG C | MPa | ASTM D790 | 3132 | 3325 | 3356 | 3361 |
| Izod notched Izod impact strength/23 DEG C | J/m | ASTM D256 | 46 | 45 | 40 | 42 |
| Flame retardant resistance 0.4mm | --- | UL 94 | V-0 | V-0 | V-0 | V-0 |
| GWIT：3.0mm | ℃ | IEC 60695-2-13 | 700 | 700 | 700 | 700 |
| GWIT：3.0mm | ℃ | IEC 60695-2-12 | 960 | 960 | 960 | 960 |
| Outward appearance | --- | --- | Porcelain is white, bright and clean, glossy | Porcelain is white, bright and clean, glossy | Porcelain is white, bright and clean, glossy | Porcelain is white, bright and clean, glossy |
Table 2
Master batch 20%(weight ratio by obtained), relative viscosity be 3.4 PA6 resin 80%(weight ratio) and a small amount of tinting material blended, in length-to-diameter ratio be 28 ~ 56:1 single screw extrusion machine on directly to extrude specification be 15.8mm × 21.0mm(internal diameter × external diameter) corrugated tube, extrusion temperature 230 ~ 240 DEG C, extrusion and pipe features and pure PA6 pipe contrast as shown in table 3:
| Project | Condition | Pure PA6 pipe | Coextrusion flame-proof PA 6 pipe |
| Extruded velocity | --- | 100% | 92.4% |
| Tube wall outward appearance | --- | Bright and clean glossy | Bright and clean, glossiness is slightly poor |
| Tubing proportion | --- | 1.14 | 1.19 |
| UV-B yellowness index | 24h | 57.3 | 49.8 |
| Mechanical property conservation rate after thermal ageing | 180℃，12h | 42.3% | 67.2% |
| Vertical combustion | UL 94 | HB | V-0 |
Table 3
According to the elaboration in above specification sheets, those skilled in the art in the invention can also carry out suitable change and amendment to above-mentioned embodiment.Therefore, the content mentioned in above-described embodiment is not limitation of the invention, and under the prerequisite not departing from inventive concept of the present invention, any apparent replacement is all within protection scope of the present invention.
Claims (1)
1. a preparation method for Special halogen-free flame-retardant master batch for nylon, described master batch is made up of the following raw material measured by weight percentage: PA6 resin 20 ~ 48%, nitrogenated flame retardant 50 ~ 70%, primary antioxidant 0.4 ~ 2.0%, auxiliary antioxidant 0.6 ~ 3.0%, external lubricant 0.8 ~ 3.0% and internal lubricant 0.2 ~ 2.0%; Wherein,
The relative viscosity of described PA6 resin is 1.7 ~ 2.8;
Described nitrogenated flame retardant is MCA fire retardant,
shouldmCA fire retardant is through dry powder prilling, and the particle diameter of MCA fire retardant is 0.1 ~ 4mm;
Described primary antioxidant is the combination of any one or several in oxidation inhibitor 1098, antioxidant 1010 and oxidation inhibitor 1024;
Described auxiliary antioxidant is the combination of any one or several in oxidation inhibitor 412S, irgasfos 168, anti-oxidant DLTP and oxidation inhibitor DSTP;
Described external lubricant is the combination of any one or several in silicone based lubricant, calcium stearate and Zinic stearas;
Described internal lubricant is the combination of any one or several in polyamide wax, montanin wax, EBS and TAF;
The preparation of this master batch comprises the following steps:
1) by PA6 resin dry 6 ~ 12h at the temperature of 90 ~ 100 DEG C, to the water content of PA6 resin lower than 0.1%;
2) by nitrogenated flame retardant dry 4 ~ 8h at the temperature of 110 ~ 120 DEG C, to the water content of nitrogenated flame retardant lower than 0.05%;
3) take the raw material of formula ratio, other raw materials outside removing fire retardant are mixed, and stirs;
4) added in parallel dual-screw extruding machine by the raw material after mixing through step 3) and carry out melt blending and extrude, in the feeding of side, add nitrogenated flame retardant, the temperature in each district of parallel dual-screw extruding machine controls between 230 ~ 240 DEG C simultaneously;
5) use direct cutting type underwater granule cutter to carry out pelletizing to the material after step 4), after cooling, dehydration, oven dry, sieving technology, obtain Special halogen-free flame-retardant master batch for nylon.
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| CN108424639A (en) * | 2018-03-13 | 2018-08-21 | 苏州银禧科技有限公司 | Dedicated modified nylon 6 material of a kind of automobile halogen-free flameproof thermostabilization bellows and preparation method thereof |
| CN112409785B (en) * | 2019-08-21 | 2022-11-04 | 青岛瑞益信新材料科技有限公司 | Halogen-free flame-retardant nylon material and preparation method thereof |
| CN111251494B (en) * | 2020-01-21 | 2022-03-29 | 天津利安隆新材料股份有限公司 | Preparation method of low-melting-point weather-resistant auxiliary agent master batch |
| CN111574828A (en) * | 2020-06-30 | 2020-08-25 | 上海芷燃新材料有限公司 | Nylon halogen-free flame-retardant master batch and preparation method thereof |
| CN113427667A (en) * | 2021-07-01 | 2021-09-24 | 中山市乐力隆工程塑料有限公司 | Process for drying-free moisture removal of polyamide engineering plastic modified particles before injection molding processing |
| CN114989600B (en) * | 2022-06-20 | 2024-01-30 | 中广核俊尔(浙江)新材料有限公司 | Halogen-free flame-retardant nylon material capable of replacing PC molding highlight and scratch-resistant panel |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1605603A (en) * | 2004-02-25 | 2005-04-13 | 吴全德 | Flame retardant reinforced nylon composition and its use |
| CN102585290A (en) * | 2012-03-14 | 2012-07-18 | 济南泰星精细化工有限公司 | Method for preparing melamine cyanurate with large particle size and wide distribution |
| CN103059337A (en) * | 2012-12-03 | 2013-04-24 | 杭州捷尔思阻燃化工有限公司 | Melamine cyanurate with uniform particles, preparation method thereof and application thereof |
| CN103073515A (en) * | 2012-12-03 | 2013-05-01 | 杭州捷尔思阻燃化工有限公司 | Large-particle-size melamine cyanurate, and preparation method and application thereof |
| CN103131174A (en) * | 2011-12-05 | 2013-06-05 | 上海耐特复合材料制品有限公司 | Polyamide composite material with high glowing filament temperature and preparation method and application thereof |
| CN103242655A (en) * | 2013-05-31 | 2013-08-14 | 东莞市国立科技有限公司 | Halogen-free flame retardant PA (Polyamide) 66 plastic modified material and preparation method thereof |
| CN103351618A (en) * | 2013-06-28 | 2013-10-16 | 广东威林工程塑料有限公司 | Antistatic, halogen-free, and fire-retardant enhanced master batch dedicated for polyamide and preparation method thereof |
-
2013
- 2013-11-13 CN CN201310571215.4A patent/CN103627168B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1605603A (en) * | 2004-02-25 | 2005-04-13 | 吴全德 | Flame retardant reinforced nylon composition and its use |
| CN103131174A (en) * | 2011-12-05 | 2013-06-05 | 上海耐特复合材料制品有限公司 | Polyamide composite material with high glowing filament temperature and preparation method and application thereof |
| CN102585290A (en) * | 2012-03-14 | 2012-07-18 | 济南泰星精细化工有限公司 | Method for preparing melamine cyanurate with large particle size and wide distribution |
| CN103059337A (en) * | 2012-12-03 | 2013-04-24 | 杭州捷尔思阻燃化工有限公司 | Melamine cyanurate with uniform particles, preparation method thereof and application thereof |
| CN103073515A (en) * | 2012-12-03 | 2013-05-01 | 杭州捷尔思阻燃化工有限公司 | Large-particle-size melamine cyanurate, and preparation method and application thereof |
| CN103242655A (en) * | 2013-05-31 | 2013-08-14 | 东莞市国立科技有限公司 | Halogen-free flame retardant PA (Polyamide) 66 plastic modified material and preparation method thereof |
| CN103351618A (en) * | 2013-06-28 | 2013-10-16 | 广东威林工程塑料有限公司 | Antistatic, halogen-free, and fire-retardant enhanced master batch dedicated for polyamide and preparation method thereof |
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