CN104017355A - Reinforced nylon with high CTI (comparative tracking index) value and good flame retardance and preparation method thereof - Google Patents

Reinforced nylon with high CTI (comparative tracking index) value and good flame retardance and preparation method thereof Download PDF

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CN104017355A
CN104017355A CN201410017625.9A CN201410017625A CN104017355A CN 104017355 A CN104017355 A CN 104017355A CN 201410017625 A CN201410017625 A CN 201410017625A CN 104017355 A CN104017355 A CN 104017355A
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temperature
district
antioxidant
nylon
flame retardant
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穆云
杨阿微
杨贤福
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WENZHOU JUXING PETROCHEMISTRY CO Ltd
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WENZHOU JUXING PETROCHEMISTRY CO Ltd
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/02Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29BPREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00Making granules
    • B29B9/12Making granules characterised by structure or composition
    • B29B9/14Making granules characterised by structure or composition fibre-reinforced
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29BPREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00Mixing; Kneading
    • B29B7/30Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/58Component parts, details or accessories; Auxiliary operations
    • B29B7/72Measuring, controlling or regulating
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29BPREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00Making granules
    • B29B9/12Making granules characterised by structure or composition
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25Component parts, details or accessories; Auxiliary operations
    • B29C48/36Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/395Means 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
    • B29C48/40Means 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25Component parts, details or accessories; Auxiliary operations
    • B29C48/92Measuring, controlling or regulating
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/01Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/016Flame-proofing or flame-retarding additives
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    • C08K5/0008Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0066Flame-proofing or flame-retarding additives
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00Use of ingredients characterised by shape
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    • C08K7/14Glass
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
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    • C09K21/00Fireproofing materials
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29BPREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00Mixing; Kneading
    • B29B7/30Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/34Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
    • B29B7/38Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
    • B29B7/46Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29BPREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00Making granules
    • B29B9/02Making granules by dividing preformed material
    • B29B9/06Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00Indexing scheme relating to extrusion moulding
    • B29C2948/92Measuring, controlling or regulating
    • B29C2948/92504Controlled parameter
    • B29C2948/92514Pressure
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00Indexing scheme relating to extrusion moulding
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    • C08L2201/00Properties
    • C08L2201/02Flame or fire retardant/resistant
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    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/18Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen

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  • Health & Medical Sciences (AREA)
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  • Medicinal Chemistry (AREA)
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Abstract

The invention discloses nylon with high CTI (comparative tracking index) value and good flame retardance and a preparation method thereof. The nylon is prepared from the following raw materials by weight percent: 18%-22% of PA6618, 28%-32% of PA6, 12%-14% of brominated polystyrene, 1.9%-2.1% of zinc borate, 29%-31% of glass fibers, 0.1%-0.2% of antioxidant 1010, 0.1%-0.2% of antioxidant 1068, 0.4%-0.6% of calcium stearate, 4.0%-5.0% of antimony sesquioxide and 7.0%-8.0% of halogen-free flame retardant synergist. The preparation method comprises the following steps: mixing PA6618, PA6, brominated polystyrene, zinc borate, the antioxidant 1010, the antioxidant 1068, calcium stearate, antimony sesquioxide and the halogen-free flame retardant synergist, adding a mixture into a high-speed stirring pot, stirring at high speed and room temperature for 5 minutes, adding stirred raw materials into a double-screw extruder, adding the glass fibers, discharging, bracing, cooling by water, dicing, drying, and packaging. The nylon is relatively good in flame retardance and relatively high in CTI value.

Description

High CTI value high flame retardant Reinforced Nylon and preparation method thereof
Technical field
The present invention relates to a kind of high CTI value high flame retardant Reinforced Nylon, also relate to the preparation method of this high CTI value high flame retardant Reinforced Nylon.
Background technology
Nylon is polyamide resin, and its amide group has polarity, has firmly hydrogen bond in its structure, makes the fusing point of nylon higher, has good mechanical property.Along with the light-weighted process of miniaturization, the high performance of electronic electric equipment, mechanical means of automobile is accelerated, to more Gao Geng great of the demand of nylon.Particularly nylon, as structural material, has proposed very high requirement to aspects such as its flame retardant resistance, resistance to tracking index valuies (CTI).
But lower, the resistance to tracking index value of existing nylon flame retardant resistance (CTI) is not high, cannot meet the service requirements of engineering equipment or electronic electric equipment, as high-end case for circuit breaker, its high-tension Working environment is in the time cutting off circuit, having electric arc produces, if the flame retardant resistance of shell and CTI are not high, not only affect the work-ing life of isolating switch, and easily caused the potential safety hazards such as fire.
Summary of the invention
The deficiency existing for prior art, the object of the present invention is to provide a kind of nylon with high flame retardant and high CTI value and preparation method thereof.
For achieving the above object, the invention provides following technical scheme: a kind of high CTI value high flame retardant Reinforced Nylon, by weight percentage, its component and content are:
PA66: 18%-22%
PA6: 28%-32%
Brominated Polystyrene: 12%-14%
Zinc borate: 1.9%-2.1%
Glass fibre: 29%-31%
Antioxidant 1010: 0.1%-0.2%
Oxidation inhibitor 1068:0.1%-0.2%
Calcium stearate: 0.4%-0.6%
Antimonous oxide: 4.0%-5.0%
Halogen-free flame retardants synergist: 7.0%-8.0%.
A method of preparing described high CTI value high flame retardant Reinforced Nylon, comprises the steps:
(1) press content proportioning by PA66, PA6, brominated Polystyrene, zinc borate, antioxidant 1010, oxidation inhibitor 1068, calcium stearate, antimonous oxide, halogen-free flame retardants synergist, add high-speed stirring pot, rotating speed is controlled at 400-500r/min, stirs 5 minutes under room temperature environment;
(2) raw material being stirred is added to twin screw extruder, add glass fibre to twin screw extruder again, temperature in twin screw extruder is respectively: 255 DEG C of district's temperature, 255 DEG C of two district's temperature, 255 DEG C of three district's temperature, 250 DEG C of four district's temperature, 250 DEG C of five district's temperature, 245 DEG C of six district's temperature, 240 DEG C of seven district's temperature, 240 DEG C of eight district's temperature, die head temperature is 250 DEG C, vacuum pressure >=0.08pa, after discharging, tie rod is crossed water cooling, pelletizing, dry, packaging.
The advantages such as brominated Polystyrene has high flame retardant, thermostability and good electrical property, and dispersiveness and compatibility are good in superpolymer, is easy to processing, non-blooming, its good electrical property can improve the CTI value of this nylon.
Glass fibre has good thermotolerance and higher physical strength, can increase accordingly resistance toheat and the intensity of this nylon.
Zinc borate has high thermal stability, can effectively improve the flame retardant properties of nylon, and the feature such as nontoxic, low water solubility, granularity is little, proportion is little, good dispersity, and environmental protection easily processing again, has reduced the injury to processing staff greatly.
Antioxidant 1010 is a kind of hindered phenol antioxygen of high molecular, and volatility is very low, and is difficult for migration, and resistance to extraction, can improve the antioxygen property of this nylon, can effectively extend the work-ing life of goods; Antioxidant 1010 is also a kind of processing stabilizers efficiently simultaneously, can improve the discoloration-resistant of polymer materials under high temperature process condition.
Oxidation inhibitor 1068 is composite products of antioxidant 1010 and irgasfos 168, and compound oxidation inhibitor 1068 has lower cost, better than the antioxidant effect of independent use irgasfos 168 or antioxidant 1010.
Calcium stearate can increase the workability of this nylon in the time of extrusion moulding and compression moulding, makes nylon molding more laborsaving, greatly reduces production difficulty, has improved production efficiency.
There are good synergistic effect antimonous oxide and above-mentioned brominated Polystyrene used time, and flame retardant effect obviously improves.Improve greatly the flame retardant properties of this nylon.
Halogen-free flame retardants synergist is mainly taking nitrogen system, phosphorus series compound and metal hydroxides as main, non-volatile when burning, do not produce corrosive gases, safety and environmental protection, and it can coordinate with other fire retardant, coordinate performance, has improved again CTI value when improving flame retardant resistance.
The invention has the beneficial effects as follows: brominated Polystyrene and zinc borate all have high flame retardant, thermostability and electrical property, can improve flame retardant resistance and the CTI value of this nylon, add antimonous oxide to play synergistic effect with brominated Polystyrene simultaneously, obviously improve the flame retardant properties of this nylon, halogen-free flame retardants synergist can coordinate with other fire retardant, play coordinative role, make this nylon there is excellent flame retardant properties and higher CTI value.
Embodiment
Below with reference to specific embodiment, the invention will be further described, but protection scope of the present invention is not limited to this.
A kind of high CTI value high flame retardant Reinforced Nylon, by weight percentage, its component and content are:
PA66: 18%-22%
PA6: 28%-32%
Brominated Polystyrene: 12%-14%
Zinc borate: 1.9%-2.1%
Glass fibre: 29%-31%
Antioxidant 1010: 0.1%-0.2%
Oxidation inhibitor 1068:0.1%-0.2%
Calcium stearate: 0.4%-0.6%
Antimonous oxide: 4.0%-5.0%
Halogen-free flame retardants synergist: 7.0%-8.0%.
Group and the each component concentration containing for embodiment of the present invention 1-3 high CTI value high flame retardant Reinforced Nylon as shown in table 1.
Group and each component concentration that table 1 embodiment 1-3 high CTI value high flame retardant Reinforced Nylon contains
Matrix material contains component and each component concentration Embodiment 1 Embodiment 2 Embodiment 3
PA66 22% 18% 20%
PA6 28% 32% 30%
Brominated Polystyrene 12% 14% 13%
Zinc borate 1.9% 2.1% 2.0%
Glass fibre 31% 29% 30%
Antioxidant 1010 0.1% 0.2% 0.15%
Oxidation inhibitor 1068 0.2% 0.1% 0.15%
Calcium stearate 0.6% 0.4% 0.5%
Antimonous oxide 5.0% 4.5% 4.0%
Halogen-free flame retardants synergist 7.0% 7.5% 8.0%
The preparation method of this high CTI value high flame retardant Reinforced Nylon is as follows:
(1) press content proportioning by PA66, PA6, brominated Polystyrene, zinc borate, antioxidant 1010, oxidation inhibitor 1068, calcium stearate, antimonous oxide, halogen-free flame retardants synergist, add high-speed stirring pot, rotating speed is controlled at 400-500r/min, stirs 5 minutes under room temperature environment;
(2) raw material being stirred is added to twin screw extruder, add glass fibre to twin screw extruder again, temperature in twin screw extruder is respectively: 255 DEG C of district's temperature, 255 DEG C of two district's temperature, 255 DEG C of three district's temperature, 250 DEG C of four district's temperature, 250 DEG C of five district's temperature, 245 DEG C of six district's temperature, 240 DEG C of seven district's temperature, 240 DEG C of eight district's temperature, die head temperature is 250 DEG C, vacuum pressure >=0.08pa, after discharging, tie rod is crossed water cooling, pelletizing, dry, packaging.
After the nylon material of preparing according to embodiment 3 does and detects, it is reported as follows:
As can be seen from the above table, nylon material prepared by embodiment 3 850 DEG C-890 DEG C all not on fire, it has high flame resistance.

Claims (2)

1. a high CTI value high flame retardant Reinforced Nylon, is characterized in that, by weight percentage, its component and content are:
PA66: 18%-22%
PA6: 28%-32%
Brominated Polystyrene: 12%-14%
Zinc borate: 1.9%-2.1%
Glass fibre: 29%-31%
Antioxidant 1010: 0.1%-0.2%
Oxidation inhibitor 1068:0.1%-0.2%
Calcium stearate: 0.4%-0.6%
Antimonous oxide: 4.0%-5.0%
Halogen-free flame retardants synergist: 7.0%-8.0%.
2. a method of preparing high CTI value high flame retardant Reinforced Nylon claimed in claim 1, is characterized in that, comprises the steps:
(1) press content proportioning by PA66, PA6, brominated Polystyrene, zinc borate, antioxidant 1010, oxidation inhibitor 1068, calcium stearate, antimonous oxide, halogen-free flame retardants synergist, add high-speed stirring pot, rotating speed is controlled at 400-500r/min, stirs 5 minutes under room temperature environment;
(2) raw material being stirred is added to twin screw extruder, add glass fibre to twin screw extruder again, temperature in twin screw extruder is respectively: 255 DEG C of district's temperature, 255 DEG C of two district's temperature, 255 DEG C of three district's temperature, 250 DEG C of four district's temperature, 250 DEG C of five district's temperature, 245 DEG C of six district's temperature, 240 DEG C of seven district's temperature, 240 DEG C of eight district's temperature, die head temperature is 250 DEG C, vacuum pressure >=0.08pa, after discharging, tie rod is crossed water cooling, pelletizing, dry, packaging.
CN201410017625.9A 2014-01-15 2014-01-15 Reinforced nylon with high CTI (comparative tracking index) value and good flame retardance and preparation method thereof Pending CN104017355A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112759924A (en) * 2020-12-29 2021-05-07 上海日之升科技有限公司 Ultrahigh-flow high-CTI halogen-containing flame-retardant nylon material and preparation method thereof

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Publication number Priority date Publication date Assignee Title
CN112759924A (en) * 2020-12-29 2021-05-07 上海日之升科技有限公司 Ultrahigh-flow high-CTI halogen-containing flame-retardant nylon material and preparation method thereof

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