CN110305474A - A kind of low temperature resistant flame retardant polyamide compoiste material and preparation method thereof - Google Patents

A kind of low temperature resistant flame retardant polyamide compoiste material and preparation method thereof Download PDF

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CN110305474A
CN110305474A CN201910520055.8A CN201910520055A CN110305474A CN 110305474 A CN110305474 A CN 110305474A CN 201910520055 A CN201910520055 A CN 201910520055A CN 110305474 A CN110305474 A CN 110305474A
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polyamide
parts
low temperature
fire
temperature resistant
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任艳丽
王洋
徐雅
张春晖
李东方
刘任晖
张奎明
张炎斌
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PINGDINGSHAN HUABANG ENGINEERING PLASTIC Co Ltd
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PINGDINGSHAN HUABANG ENGINEERING PLASTIC Co Ltd
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    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00Processes of treating or compounding macromolecular substances
    • C08J3/20Compounding polymers with additives, e.g. colouring
    • C08J3/22Compounding polymers with additives, e.g. colouring using masterbatch techniques
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    • C08J2377/00Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
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    • C08J2423/00Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
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    • C08J2451/00Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2451/06Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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    • C08J2477/00Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2477/02Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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    • C08J2477/00Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
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    • C08J2483/00Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
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    • C08K13/00Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
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    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
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    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
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Abstract

The invention discloses a kind of low temperature resistant flame retardant polyamide compoiste materials and preparation method thereof, the polyamide compoiste material is made of polyamide substrate, fire-retardant master granule, modified filler, compatilizer, antioxidant, by weight, polyamide substrate account for 70-75 parts, fire-retardant master granule account for 8-15 parts, modified filler account for 7-10 parts, compatilizer account for 5-8 parts, antioxidant account for 0.5-1 parts;The polyamide substrate is to be made of the polyamide 66 and polyamide 6 of weight ratio 3:1;The fire-retardant master granule is made of polyamide 66, polypropylene and red phosphorus;The modified filler by weight, is made of 1 kaolin, alumina powder and modified manometer silicon dioxide, 6 carbide fine powders.Polyamide compoiste material prepared by the present invention has good intensity and certain toughness, while polyamide compoiste material prepared by the present invention has good flame-retardance energy, furthermore, polyamide compoiste material appearance produced by the present invention is good.

Description

A kind of low temperature resistant flame retardant polyamide compoiste material and preparation method thereof
Technical field
The invention belongs to the modified manufacture fields of polyamide material, specifically design a kind of low temperature resistant flame retardant polyamide compoiste material And preparation method thereof.
Background technique
Polyamide material have many advantages, such as intensity is high, acidproof, non-aging, insulating properties and widely used, however Polyamide use temperature range is relatively narrow, it is common to use temperature is -20 DEG C -80 DEG C, and which has limited the application fields of polyamide material. Low temperature resistant modified nylon materials mainly have compared with lower glass transition temperatures component by adding in nylon resin as toughening Agent, toughener usually have following several: 1. polyolefin elastomer and its graft (POE);2. ethylene propylene diene rubber (EPDM);③ The maleic anhydride grafts (PE-g-MAH) of polyethylene;4. styrene butadiene thermoplasticelastomer (SBS);5. sarin resin (Surlyn);6. the copolymer of acrylate or salt;7. ethylene-acrylate-copolymer-maleic anhydride etc..Above-mentioned toughener The low-temperature flexibility of nylon can be effectively improved, but there is also a common defect, i.e., the introducing of above-mentioned toughener can all drop The flame retardant rating of low nylon base.
Patent No. CN104829832A discloses a kind of preparation method of organic-silicon-modified flame-retardant nylon 66, that is, will be imperial when polymerizeing It is copolymerized with organosilicon modifier, obtains flame retardant type casting nylon composite materials;Patent No. 104974504A discloses one kind By the fire-retardant nylon composite material of nylon resin and the preparation of organic-silicon-modified resin.
Summary of the invention
In order to solve the above technical problems, the present invention proposes a kind of low temperature resistant flame retardant polyamide compoiste material and its preparation side Method improves the resistance to low temperature and flame retardant property of polyamide.
To achieve the above object, the technical solution adopted by the present invention are as follows: a kind of low temperature resistant flame retardant polyamide compoiste material, by Polyamide substrate, fire-retardant master granule, modified filler, compatilizer, antioxidant are made, and by weight, polyamide substrate accounts for 70-75 Part, fire-retardant master granule account for 8-15 parts, modified filler account for 7-10 parts, compatilizer account for 5-8 parts, antioxidant account for 0.5-1 parts;The polyamides Amido body is to be made of the polyamide 66 and polyamide 6 of weight ratio 3:1;It is 15:5-3:2's that the fire-retardant master granule, which is by weight ratio, Polyamide 66, polypropylene and red phosphorus composition;The modified filler by weight, is not surpassed by 10-15 parts of kaolin, 4-6 parts of fineness It is thin no more than 10 microns of silicon carbide to cross 5 microns of alumina powder and 5-7 parts of modified manometer silicon dioxide, 6-8 part fineness Powder composition, wherein the modified manometer silicon dioxide is that commercially available nano silica is mixed with the surface treating agent of its weight 3-4% Obtain, the surface treating agent by barium hydroxide, sodium chloride and KH550 according to weight ratio 3-4:1-2:30 ratio mixing and At;The compatilizer is POE, and the antioxidant is made of the 168 of weight ratio 1:1.5 and 1010.
Further, also contain maleic anhydride inoculated polypropylene in the fire-retardant master granule, wherein weight is equivalent to polyamide 0.5 times.
Further, 3-4 parts of silicone powders are also contained in the modified filler.
Further, 0.5-0.8 parts of modified montmorillonoids have been additionally added in the modified filler, the modified montmorillonoid is by matter Amount is mixed than the montmorillonite for being 8-5:1 and KBr.
Further, the calcium carbonate powder for being also 5-10 microns containing 0.3-0.5 parts of partial sizes in the modified filler.
Further, polyamide compoiste material contains 3-6 parts of modification medium powder, and the modification medium powder is passed through by pulpous state diatom ooze Calcium hydroxide after drying, crushing with 2 times of pulpous state diatomite weight mixes.
Further, preparing the low temperature resistant flame retardant polyamide compoiste material method is to require according to the above ratio, first with double Fire-retardant master granule raw material is kneaded by roller open mill, discharging, and fire-retardant master granule is made with broken crusher machine, for use;Then by it is above-mentioned to Fire-retardant master granule requires to be added with other raw materials that high-speed mixer and mixing is uniform according to the above ratio, finally mixed by after mixing It closes material to add twin-screw extrude, 200-500 revs/min of working speed of double spiral shell extruders, use twin-screw by 220-300 DEG C of temperature Extruder extruding pelletization, resulting Particles dispersed material are low temperature resistant flame retardant polyamide compoiste material.
Compared with prior art, the invention has the following advantages:
A kind of low temperature resistant flame retardant polyamide compoiste material prepared by the present invention and preparation method thereof, on the one hand it is in subzero 50 DEG C of items Part lower has good intensity and certain toughness, while polyamide compoiste material prepared by the present invention has good flame-retardance Can, furthermore, polyamide compoiste material appearance produced by the present invention is good.
Specific embodiment
Below with reference to the preferred embodiments of the present invention will be described in detail, so that advantages and features of the invention can be easier to In being readily appreciated by one skilled in the art, so as to make a clearer definition of the protection scope of the present invention.
Embodiment 1
A kind of low temperature resistant flame retardant polyamide compoiste material, by polyamide substrate, fire-retardant master granule, modified filler, compatilizer, anti-oxidant Agent is made, by weight, polyamide substrate account for 70 parts, fire-retardant master granule account for 8 parts, modified filler account for 7 parts, compatilizer account for 5 parts, antioxygen Agent accounts for 0.5 part;The polyamide substrate is to be made of the polyamide 66 and polyamide 6 of weight ratio 3:1;The fire-retardant master granule is It is made of polyamide 66, polypropylene and red phosphorus that weight ratio is 15:5:2;The modified filler by weight, by 10 parts of kaolinites Soil, 4 parts of fineness are no more than 5 microns of alumina powder and 5 parts of modified manometer silicon dioxide, 6 parts of fineness are no more than 10 microns Carbide fine powder, wherein the modified manometer silicon dioxide be commercially available nano silica and its weight 3-4% surface treatment Agent is mixed to get, the surface treating agent by barium hydroxide, sodium chloride and KH550 according to weight ratio 3:2:30 ratio mixing and At;The compatilizer is POE, and the antioxidant is made of the 168 of weight ratio 1:1.5 and 1010.
Further, also contain maleic anhydride inoculated polypropylene in the fire-retardant master granule, wherein weight is equivalent to polyamide 0.5 times.
Further, 3 parts of silicone powders are also contained in the modified filler.
Further, 0.5 part of modified montmorillonoid has been additionally added in the modified filler, the modified montmorillonoid is by mass ratio It is mixed for the montmorillonite and KBr of 8:1.
Further, the calcium carbonate powder for being also 5-10 microns containing 0.3 part of partial size in the modified filler.
Further, polyamide compoiste material contains 3 parts of modification medium powder, and the modification medium powder is by pulpous state diatom ooze through drying Calcium hydroxide dry, after crushing with 2 times of pulpous state diatomite weight mixes.
Further, preparing the low temperature resistant flame retardant polyamide compoiste material method is to require according to the above ratio, first with double Fire-retardant master granule raw material is kneaded by roller open mill, discharging, and fire-retardant master granule is made with broken crusher machine, for use;Then by it is above-mentioned to Fire-retardant master granule requires to be added with other raw materials that high-speed mixer and mixing is uniform according to the above ratio, finally mixed by after mixing It closes material to add twin-screw extrude, double 300 revs/min of spiral shell extruder working speed, 280 DEG C of temperature, be squeezed with double screw extruder It is granulated out, resulting Particles dispersed material is low temperature resistant flame retardant polyamide compoiste material.
Embodiment 2
A kind of low temperature resistant flame retardant polyamide compoiste material, by polyamide substrate, fire-retardant master granule, modified filler, compatilizer, anti-oxidant Agent is made, by weight, polyamide substrate account for 72 parts, fire-retardant master granule account for 10 parts, modified filler account for 8 parts, compatilizer account for 6 parts, it is anti- Oxidant accounts for 0.8 part;The polyamide substrate is to be made of the polyamide 66 and polyamide 6 of weight ratio 3:1;The fire-retardant master granule For be 15:4:2 by weight ratio polyamide 66, polypropylene and red phosphorus form;The modified filler by weight, by 13 parts of kaolinites Soil, 5 parts of fineness are no more than 5 microns of alumina powder and 6 parts of modified manometer silicon dioxide, 7 parts of fineness are no more than 10 microns Carbide fine powder, wherein the modified manometer silicon dioxide be commercially available nano silica and its weight 3% surface treating agent Be mixed to get, the surface treating agent by barium hydroxide, sodium chloride and KH550 according to weight ratio 4:1:30 ratio mixing and At;The compatilizer is POE, and the antioxidant is made of the 168 of weight ratio 1:1.5 and 1010.
Further, also contain maleic anhydride inoculated polypropylene in the fire-retardant master granule, wherein weight is equivalent to polyamide 0.5 times.
Further, 3 parts of silicone powders are also contained in the modified filler.
Further, 0.7 part of modified montmorillonoid has been additionally added in the modified filler, the modified montmorillonoid is by mass ratio It is mixed for the montmorillonite and KBr of 7:1.
Further, the calcium carbonate powder for being also 5-10 microns containing 0.4 part of partial size in the modified filler.
Further, polyamide compoiste material contains 5 parts of modification medium powder, and the modification medium powder is by pulpous state diatom ooze through drying Calcium hydroxide dry, after crushing with 2 times of pulpous state diatomite weight mixes.
Further, preparing the low temperature resistant flame retardant polyamide compoiste material method is to require according to the above ratio, first with double Fire-retardant master granule raw material is kneaded by roller open mill, discharging, and fire-retardant master granule is made with broken crusher machine, for use;Then by it is above-mentioned to Fire-retardant master granule requires to be added with other raw materials that high-speed mixer and mixing is uniform according to the above ratio, finally mixed by after mixing It closes material to add twin-screw extrude, double 300 revs/min of spiral shell extruder working speed, 280 DEG C of temperature, be squeezed with double screw extruder It is granulated out, resulting Particles dispersed material is low temperature resistant flame retardant polyamide compoiste material.
Embodiment 3
A kind of low temperature resistant flame retardant polyamide compoiste material, by polyamide substrate, fire-retardant master granule, modified filler, compatilizer, anti-oxidant Agent is made, by weight, polyamide substrate account for 75 parts, fire-retardant master granule account for 15 parts, modified filler account for 10 parts, compatilizer account for 8 parts, it is anti- Oxidant accounts for 1 part;The polyamide substrate is to be made of the polyamide 66 and polyamide 6 of weight ratio 3:1;The fire-retardant master granule is It is made of polyamide 66, polypropylene and red phosphorus that weight ratio is 15:3:2;The modified filler by weight, by 15 parts of kaolinites Soil, 6 parts of fineness are no more than 5 microns of alumina powder and 7 parts of modified manometer silicon dioxide, 8 parts of fineness are no more than 10 microns Carbide fine powder, wherein the modified manometer silicon dioxide be commercially available nano silica and its weight 4% surface treating agent Be mixed to get, the surface treating agent by barium hydroxide, sodium chloride and KH550 according to weight ratio 2:1:15 ratio mixing and At;The compatilizer is POE, and the antioxidant is made of the 168 of weight ratio 1:1.5 and 1010.
Further, also contain maleic anhydride inoculated polypropylene in the fire-retardant master granule, wherein weight is equivalent to polyamide 0.5 times.
Further, 4 parts of silicone powders are also contained in the modified filler.
Further, 0.8 part of modified montmorillonoid has been additionally added in the modified filler, the modified montmorillonoid is by mass ratio It is mixed for the montmorillonite and KBr of 5:1.
Further, the calcium carbonate powder for being also 5-10 microns containing 0.5 part of partial size in the modified filler.
Further, polyamide compoiste material contains 6 parts of modification medium powder, and the modification medium powder is by pulpous state diatom ooze through drying Calcium hydroxide dry, after crushing with 2 times of pulpous state diatomite weight mixes.
Further, preparing the low temperature resistant flame retardant polyamide compoiste material method is to require according to the above ratio, first with double Fire-retardant master granule raw material is kneaded by roller open mill, discharging, and fire-retardant master granule is made with broken crusher machine, for use;Then by it is above-mentioned to Fire-retardant master granule requires to be added with other raw materials that high-speed mixer and mixing is uniform according to the above ratio, finally mixed by after mixing It closes material to add twin-screw extrude, double 300 revs/min of spiral shell extruder working speed, 280 DEG C of temperature, be squeezed with double screw extruder It is granulated out, resulting Particles dispersed material is low temperature resistant flame retardant polyamide compoiste material.
A specific embodiment of the invention, but scope of protection of the present invention is not limited thereto, it is any to be familiar with this field Within the technical scope disclosed by the invention, changes or replacements that can be thought of without creative work should all be contained technical staff Lid is within protection scope of the present invention.Therefore, protection scope of the present invention should be to protect model defined by claims Subject to enclosing.

Claims (7)

1. a kind of low temperature resistant flame retardant polyamide compoiste material, it is characterised in that: by polyamide substrate, fire-retardant master granule, modified filler, Compatilizer, antioxidant are made, and by weight, polyamide substrate accounts for 70-75 parts, fire-retardant master granule accounts for 8-15 parts, modified filler accounts for 7-10 parts, compatilizer account for 5-8 parts, antioxidant account for 0.5-1 parts;The polyamide substrate is the polyamide 66 by weight ratio 3:1 It is formed with polyamide 6;The fire-retardant master granule is that polyamide 66, polypropylene and the red phosphorus for being 15:5-3:2 by weight ratio form;Institute State modified filler by weight, alumina powder by 10-15 parts of kaolin, 4-6 parts of fineness no more than 5 microns and 5-7 parts Carbide fine powder of modified manometer silicon dioxide, 6-8 part fineness no more than 10 microns forms, wherein the modified nano-silica Silicon is that commercially available nano silica and the surface treating agent of its weight 3-4% are mixed to get, and the surface treating agent is by hydroxide Barium, sodium chloride and KH550 are mixed according to the ratio of weight ratio 3-4:1-2:30;The compatilizer is POE, described anti-oxidant Agent is made of the 168 of weight ratio 1:1.5 and 1010.
2. a kind of low temperature resistant flame retardant polyamide compoiste material according to claim 1, it is characterised in that: the fire-retardant master granule In also contain maleic anhydride inoculated polypropylene, wherein weight is equivalent to 0.5 times of polyamide.
3. a kind of low temperature resistant flame retardant polyamide compoiste material according to claim 1, it is characterised in that: the modified filler In also contain 3-4 parts of silicone powders.
4. a kind of low temperature resistant flame retardant polyamide compoiste material according to claim 1, it is characterised in that: the modified filler In be additionally added 0.5-0.8 parts of modified montmorillonoids, the modified montmorillonoid is mixed by the montmorillonite that mass ratio is 8-5:1 and KBr It closes.
5. a kind of low temperature resistant flame retardant polyamide compoiste material according to claim 1, it is characterised in that: the modification is filled out The calcium carbonate powder for being also 5-10 microns containing 0.3-0.5 parts of partial sizes in material.
6. a kind of low temperature resistant flame retardant polyamide compoiste material according to claim 1, it is characterised in that: polyamide composite wood Material contain 3-6 parts of modification medium powder, the modification medium powder by pulpous state diatom ooze after dried, crushed with pulpous state diatomite weight 2 times of calcium hydroxide mixes.
7. a kind of low temperature resistant flame retardant polyamide compoiste material according to claim 1, it is characterised in that: preparation method is It requires, is kneaded fire-retardant master granule raw material according to the above ratio first with two-roll mill, discharge, and resistance is made with broken crusher machine Master batch is fired, for use;Then above-mentioned stand-by fire-retardant master granule and other raw materials are required according to the above ratio that high-speed mixer and mixing is added Uniformly, finally mixture after mixing is added twin-screw extrude, double spiral shell extruder working speed 200-500 turns/ Point, 220-300 DEG C of temperature, with double screw extruder extruding pelletization, resulting Particles dispersed material is low temperature resistant flame retardant polyamide Composite material.
CN201910520055.8A 2019-06-21 2019-06-21 A kind of low temperature resistant flame retardant polyamide compoiste material and preparation method thereof Pending CN110305474A (en)

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CN111040445A (en) * 2019-12-31 2020-04-21 苏州旭光聚合物有限公司 Flame-retardant nylon 66/nylon 6 composite material with high mechanical property
CN112552680A (en) * 2020-12-11 2021-03-26 上海金发科技发展有限公司 Efficient flame-retardant nylon composite material and preparation method thereof
US11787939B2 (en) 2019-10-24 2023-10-17 Inv Nylon Polymers Americas, Llc Polyamide compositions and articles made therefrom

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CN106589588A (en) * 2016-12-06 2017-04-26 东莞职业技术学院 Flame-retardant enhanced-type polypropylene composite material and preparing method thereof
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US11787939B2 (en) 2019-10-24 2023-10-17 Inv Nylon Polymers Americas, Llc Polyamide compositions and articles made therefrom
CN111040445A (en) * 2019-12-31 2020-04-21 苏州旭光聚合物有限公司 Flame-retardant nylon 66/nylon 6 composite material with high mechanical property
CN112552680A (en) * 2020-12-11 2021-03-26 上海金发科技发展有限公司 Efficient flame-retardant nylon composite material and preparation method thereof

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