CN107778856A - Halogen-free flameproof high-temperature resistant nylon 46 composite and preparation method thereof - Google Patents

Halogen-free flameproof high-temperature resistant nylon 46 composite and preparation method thereof Download PDF

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Publication number
CN107778856A
CN107778856A CN201711143700.6A CN201711143700A CN107778856A CN 107778856 A CN107778856 A CN 107778856A CN 201711143700 A CN201711143700 A CN 201711143700A CN 107778856 A CN107778856 A CN 107778856A
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nylon
halogen
temperature resistant
free flameproof
resistant nylon
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梁生
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Jiangmen Rong Long New Mstar Technology Ltd
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Jiangmen Rong Long New Mstar Technology Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K2003/026—Phosphorus
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention discloses a kind of halogen-free flameproof high-temperature resistant nylon 46 composite and preparation method thereof, it is made up of following components in percentage by weight：Nylon 46 (25~25%), nylon66 fiber (15~25%), toughness reinforcing compatilizer (3~7%), halogen-free flame retardants (12~18%), glass fibre (20~30%) antioxidant (0.1~0.3%), anti-UV agent (0.3~0.7%), heat stabilizer (0.2~0.4%), glass microballoon (3~7%).When making, various raw materials are weighed by weight percentage, and the various raw materials to weighing mix；Mixed material is put into double screw extruder, extruding pelletization.The present invention is modified to nylon 46, and the nylon 46 composite for making to prepare has the characteristics of high-temperature resistant.

Description

Halogen-free flameproof high-temperature resistant nylon 46 composite and preparation method thereof
Technical field
The present invention relates to technical field of high-molecule composite preparation, more specifically, more particularly to a kind of halogen-free flameproof High-temperature resistant nylon 46 composite and preparation method thereof.
Background technology
Nylon 46 is the aliphatic amide formed by diaminobutane and hexylene glycol polycondensation, has mechanical strength Height, good toughness, endurance, have small, wear-resisting, heat-resisting, the easy modification forming of self lubricity, coefficient of friction, short molding cycle, processing warp The advantages that Ji.Nylon 46 has the performance and value for being difficult analogy in automobile and electronic application field, it is possible to provide high Very good mechanical properties under the conditions of temperature, remarkable wearability and low friction and excellent mobility so that working process is more Convenient, particular design is more flexible.
At present, the domestic modification technology to nylon 46 also compares limitation, and starting is also later, also exists much not Perfect place, it substantially can not find a kind of more feasible and simple to operate modification technology.Nylon 46 in itself by In its molecular structure, it is had higher temperature resistant grade, and molecular weight is higher, but due to its high temperature resistant, thus mobility compared with Difference, cause processing more difficult.
The content of the invention
The invention provides a kind of halogen-free flameproof high-temperature resistant nylon 46 composite and preparation method thereof, and this is multiple Condensation material specifically has high-wearing feature and the characteristic of high-temperature resistant.
The technical scheme is that：
A kind of high abrasion high-temperature resistant nylon 46 composite, is made up of following components in percentage by weight：
One kind as above technical scheme is improved, and the toughness reinforcing compatilizer is polyethylene octene copolymer elastomer-Malaysia Acid anhydride copolymer, ethylene propylene diene rubber-copolymer-maleic anhydride, polystyrene-ethylene-butylene-polystyrene-maleic anhydride are common Any one in polymers or its any a variety of combination.
One kind as above technical scheme is improved, and the halogen-free flame retardants time is phosphonate, tricresyl phosphate, red phosphorus In any a variety of combination of any one or its.
One kind as above technical scheme is improved, and the glass fibre is circular glass fiber, non-circular glass fibre In any one or both combination.
One kind as above technical scheme is improved, and described antioxidant is N, N '-hexylidene -1.6- two [(3,5- bis- uncles Butyl -4- hydroxyphenyls) propionamide], four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters, three (2,4- bis- Tert-butyl-phenyl) phosphite ester, any one or its in double (2,4- di-tert-butyl-phenyl) pentaerythritol diphosphites Anticipate a variety of combinations.
One kind as above technical scheme is improved, and the anti-UV agent is by histamine, dihydroxy benaophenonel, hydroxyphenyl benzo Any one in triazole, hydroxyphenyl-triazine or its any a variety of combination.
One kind as above technical scheme is improved, and described heat stabilizer is PolyAd HS 02.
One kind as above technical scheme is improved, and described glass microballoon is hollow glass micropearl.
The invention also provides the preparation for preparing above-mentioned halogen-free flameproof high-temperature resistant nylon 46 composite Method, comprise the following steps：
Step 1：Nylon 46 and nylon 66 resin are placed in 100 DEG C of baking oven and dry 3-4 hours, makes it Moisture content is less than 0.5%；
Step 2：By each component percentage by weight in formula weigh respectively nylon 46 resin, nylon 66 resin, Toughness reinforcing compatilizer, halogen-free flame retardants, glass fibre, antioxidant, anti-UV agent, heat stabilizer and glass microballoon；
Step 3：Nylon 46 resin, nylon 66 resin, toughness reinforcing compatilizer, antioxidant and anti-UV agent are added 2~5min is stirred in homogenizer, obtains mixture A；Halogen-free flame retardants and heat stabilizer stir in homogenizer 2~5min of mixing is mixed, obtains mixture B；Glass fibre and glass microballoon are stirred 2~5min in homogenizer, obtain To mixture C；
Step 4：The draw ratio of double screw extruder needed for production is 40: 1, configures bilateral feeding, and mixture A passes through Main feeding is added in double screw extruder, and mixture B and mixture C are added to twin-screw extrusion by two side feedings respectively Tie rod, pelletizing are extruded in machine, after melting mixing and is packed.
Compared with prior art, what the present invention obtained has the beneficial effect that：
The halogen-free flameproof high-temperature resistant nylon 46 composite of the present invention, by main material poly hexamethylene adipamide fourth The mixing of diamines and nylon66 fiber, and add halogen-free flame retardants, anti-UV agent and heat stabilizer, the composite for making to prepare and have The characteristics of high-temperature resistant, the production requirement of automobile and the high-temperature resistant of electronic application field is disclosure satisfy that, and produce the high-temperature resistant and gather oneself Two acyl butanediamine composite technologys are simple, convenient for production, financial cost is relatively low, meet the requirement of industrialized production, before market Scape is wide.
Embodiment
The specific embodiment of the present invention is described in detail below.
Embodiment 1：
A kind of high abrasion high-temperature resistant nylon 46 composite, is made up of following components in percentage by weight：
35% nylon 46；
18% nylon66 fiber；
5% toughness reinforcing compatilizer (polyethylene octene copolymer elastomer-copolymer-maleic anhydride, ethylene propylene diene rubber-maleic acid Anhydride copolymer, polystyrene-ethylene-butylene-polystyrene-maleic anhydride copolymer, mass ratio 1:1:1)；
14% halogen-free flame retardants (phosphinates, tricresyl phosphate, red phosphorus, mass ratio 1:1:1)；
23% glass fibre (circular glass fiber, non-circular glass fibre, mass ratio 2:1)；
0.3% antioxidant (N, N '-hexylidene -1.6- two [(3,5- di-t-butyl -4- hydroxyphenyls) propionamide], four [β - (3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, three (2,4- di-tert-butyl-phenyl) phosphite esters, double (2,4- Di-tert-butyl-phenyl) pentaerythritol diphosphites, mass ratio 1:1:1:1)；
0.3% anti-UV agent is (by histamine, dihydroxy benaophenonel, hydroxy-phenyl benzotriazole, hydroxyphenyl-triazine, mass ratio 1: 1:1:1),
0.4% heat stabilizer (PolyAd HS 02)；
4% glass microballoon (hollow glass micropearl).
It is nylon 46 resin (moisture 1 ‰) after first drying, nylon 66 resin (moisture 1 ‰), poly- Ethylene octene copolymer elastomer-copolymer-maleic anhydride, ethylene propylene diene rubber-copolymer-maleic anhydride, polystyrene-ethylene- Butylene-polystyrene-maleic anhydride copolymer, N, N '-hexylidene -1.6- two [(3,5- di-t-butyl -4- hydroxyphenyls) propionyl Amine], four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters, three (2,4- di-tert-butyl-phenyl) phosphorous acid Ester, double (2,4- di-tert-butyl-phenyl) pentaerythritol diphosphites, by histamine, dihydroxy benaophenonel, hydroxy-phenyl benzotriazole Stirred in the homogenizer being added to hydroxyphenyl-triazine on main drawing-in device, the mixture to stir is added to In the main feeding machine of double screw extruder, phosphinates, tricresyl phosphate, red phosphorus and PolyAd HS 02 are added to 1# sides Stirred in homogenizer on drawing-in device, the 1# sides that the mixture to stir is added to double screw extruder are fed In material machine, the 2# sides that circular glass fiber, non-circular glass fibre and hollow glass micropearl are added to double screw extruder are fed In glassware, it is granulated through double screw extruder, engine speed 400-600r/min, vacuum pressure is controlled in 0.06-0.08Mpa.
Embodiment 2：
A kind of high abrasion high-temperature resistant nylon 46 composite, is made up of following components in percentage by weight：
25% nylon 46；
20% nylon66 fiber；
7% toughness reinforcing compatilizer (polyethylene octene copolymer elastomer-copolymer-maleic anhydride)；
16% halogen-free flame retardants (phosphinates)；
26% glass fibre (circular glass fiber)；
0.2% antioxidant (N, N '-hexylidene -1.6- two [(3,5- di-t-butyl -4- hydroxyphenyls) propionamide])；
0.5% anti-UV agent (by histamine),
0.3% heat stabilizer (PolyAd HS 02)；
5% glass microballoon (hollow glass micropearl).
Nylon 46 resin (moisture 1 ‰), nylon 66 resin (moisture 1 ‰), 3kg after first drying Polyethylene octene copolymer elastomer-copolymer-maleic anhydride, N, N '-hexylidene -1.6- two [(3,5- di-t-butyl -4- oxybenzenes Base) propionamide], stirred in by the homogenizer that histamine is added on main drawing-in device, the mixture that will be stirred It is added in the main feeding machine of double screw extruder, phosphinates and PolyAd HS 02 is added on the drawing-in device of 1# sides Stir, the mixture to stir is added in the 1# sides feeding machine of double screw extruder, by circle in homogenizer Shape glass fibre and hollow glass micropearl are added in the 2# sides feeder of double screw extruder, are granulated through double screw extruder, Engine speed 400-600r/min, vacuum pressure are controlled in 0.06-0.08Mpa.
Embodiment 3：
A kind of high abrasion high-temperature resistant nylon 46 composite, is made up of following components in percentage by weight：
28% nylon 46；
20% nylon66 fiber；
6% toughness reinforcing compatilizer (polyethylene octene copolymer elastomer-copolymer-maleic anhydride, ethylene propylene diene rubber-maleic acid Anhydride copolymer, mass ratio 1:1)；
14% halogen-free flame retardants (phosphinates, tricresyl phosphate, mass ratio 1:1)；
25% glass fibre (non-circular glass fibre)；
0.15% antioxidant (N, N '-hexylidene -1.6- two [(3,5- di-t-butyl -4- hydroxyphenyls) propionamide], four [β - (3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, mass ratio 1:1)；
0.55% anti-UV agent is (by histamine, dihydroxy benaophenonel, mass ratio 1:1),
0.3% heat stabilizer (PolyAd HS 02)；
6% glass microballoon (hollow glass micropearl).
It is nylon 46 resin (moisture 1 ‰) after first drying, nylon 66 resin (moisture 1 ‰), poly- Ethylene octene copolymer elastomer-copolymer-maleic anhydride, ethylene propylene diene rubber-copolymer-maleic anhydride, N, N '-hexylidene- 1.6- bis- [(3,5- di-t-butyl -4- hydroxyphenyls) propionamide], four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] seasons penta Four alcohol esters, stir, will stir in by the homogenizer that histamine, dihydroxy benaophenonel are added on main drawing-in device Mixture be added in the main feeding machine of double screw extruder, by phosphinates, tricresyl phosphate, PolyAd HS 02 plus Enter into the homogenizer on the drawing-in device of 1# sides and stir, the mixture to stir is added to double screw extruder 1# sides feeding machine in, non-circular glass fibre and hollow glass micropearl are added to the 2# sides feeder of double screw extruder In, it is granulated through double screw extruder, engine speed 400-600r/min, vacuum pressure is controlled in 0.06-0.08Mpa.
Embodiment 4：
A kind of high abrasion high-temperature resistant nylon 46 composite, is made up of following components in percentage by weight：
30% nylon 46；
23% nylon66 fiber；
4% toughness reinforcing compatilizer (polyethylene octene copolymer elastomer-copolymer-maleic anhydride, polystyrene-ethylene-butylene- Polystyrene-maleic anhydride copolymer, mass ratio 1:1)；
15% halogen-free flame retardants (phosphinates, red phosphorus, mass ratio 1:1)；
22% glass fibre (circular glass fiber)；
0.1% antioxidant (N, N '-hexylidene -1.6- two [(3,5- di-t-butyl -4- hydroxyphenyls) propionamide], four [β - (3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, three (2,4- di-tert-butyl-phenyl) phosphite esters, mass ratio For 1:1:2)；
0.6% anti-UV agent is (by histamine, hydroxy-phenyl benzotriazole, hydroxyphenyl-triazine, mass ratio 1:1:2),
0.3% heat stabilizer (PolyAd HS 02)；
5% glass microballoon (hollow glass micropearl).
It is nylon 46 resin (moisture 1 ‰) after first drying, nylon 66 resin (moisture 1 ‰), poly- Ethylene octene copolymer elastomer-copolymer-maleic anhydride, polystyrene-ethylene-butylene-polystyrene-maleic anhydride copolymer, N, N '-hexylidene -1.6- two [(3,5- di-t-butyl -4- hydroxyphenyls) propionamide], four [β-(3,5- di-t-butyl -4- hydroxy benzenes Base) propionic acid] pentaerythritol ester, three (2,4- di-tert-butyl-phenyl) phosphite esters, by histamine, hydroxy-phenyl benzotriazole, hydroxyphenyl Stirred in the homogenizer that triazine is added on main drawing-in device, the mixture to stir is added into twin-screw squeezes Go out in the main feeding machine of machine, phosphinates, red phosphorus and PolyAd HS 02 are added to the high-speed stirred on the drawing-in device of 1# sides Stirred in machine, the mixture to stir is added in the 1# sides feeding machine of double screw extruder, circular glass is fine Peacekeeping hollow glass micropearl is added in the 2# sides feeder of double screw extruder, is granulated through double screw extruder, engine speed 400-600r/min, vacuum pressure are controlled in 0.06-0.08Mpa.
Embodiment 5：
A kind of high abrasion high-temperature resistant nylon 46 composite, is made up of following components in percentage by weight：
32% nylon 46；
18% nylon66 fiber；
6% toughness reinforcing compatilizer (ethylene propylene diene rubber-copolymer-maleic anhydride, polystyrene-ethylene-butylene-polyphenyl second Alkene-copolymer-maleic anhydride, mass ratio 1:1)；
17% halogen-free flame retardants (tricresyl phosphate, red phosphorus, mass ratio 1:1)；
23% glass fibre (circular glass fiber, non-circular glass fibre, mass ratio 1:1)；
0.2% antioxidant (N, N '-hexylidene -1.6- two [(3,5- di-t-butyl -4- hydroxyphenyls) propionamide], four [β - (3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, double (2,4- di-tert-butyl-phenyl) pentaerythrite diphosphorous acids Ester, mass ratio 1:1:3)；
0.5% anti-UV agent is (by histamine, dihydroxy benaophenonel, hydroxyphenyl-triazine, mass ratio 1:1:2),
0.3% heat stabilizer (PolyAd HS 02)；
3% glass microballoon (hollow glass micropearl).
Nylon 46 resin (moisture 1 ‰), nylon 66 resin (moisture 1 ‰), three after first drying First EP rubbers-copolymer-maleic anhydride, polystyrene-ethylene-butylene-polystyrene-maleic anhydride copolymer, N, N '-Asia Hexyl -1.6- two [(3,5- di-t-butyl -4- hydroxyphenyls) propionamide], four [β-(3,5- di-tert-butyl-hydroxy phenyl) third Acid] pentaerythritol ester, double (2,4- di-tert-butyl-phenyl) pentaerythritol diphosphites, by histamine, dihydroxy benaophenonel, oxybenzene Stirred in the homogenizer that base triazine is added on main drawing-in device, the mixture to stir is added to twin-screw In the main feeding machine of extruder, tricresyl phosphate, red phosphorus and PolyAd HS 02 are added to the height on the drawing-in device of 1# sides Stir, the mixture to stir is added in the 1# sides feeding machine of double screw extruder, by circle in fast mixer Glass fibre, non-circular glass fibre and hollow glass micropearl are added in the 2# sides feeder of double screw extruder, through double spiral shells Bar extruder is granulated, engine speed 400-600r/min, and vacuum pressure is controlled in 0.06-0.08Mpa.
Embodiment 6：
A kind of high abrasion high-temperature resistant nylon 46 composite, is made up of following components in percentage by weight：
29% nylon 46；
16% nylon66 fiber；
4% toughness reinforcing compatilizer (polyethylene octene copolymer elastomer-copolymer-maleic anhydride, polystyrene-ethylene-butylene- Polystyrene-maleic anhydride copolymer, mass ratio 1:1)；
18% halogen-free flame retardants (tricresyl phosphate, red phosphorus, mass ratio 1:2)；
26% glass fibre (circular glass fiber, non-circular glass fibre, mass ratio 3:2)；
0.3% antioxidant (three (2,4- di-tert-butyl-phenyl) phosphite esters, double (2,4- di-tert-butyl-phenyl) pentaerythrites Diphosphites, mass ratio 1:1)；
0.5% anti-UV agent (dihydroxy benaophenonel, hydroxy-phenyl benzotriazole, hydroxyphenyl-triazine, mass ratio 1:1:1),
0.2% heat stabilizer (PolyAd HS 02)；
6% glass microballoon (hollow glass micropearl).
It is nylon 46 resin (moisture 1 ‰) after first drying, nylon 66 resin (moisture 1 ‰), poly- Ethylene octene copolymer elastomer-copolymer-maleic anhydride, polystyrene-ethylene-butylene-polystyrene-maleic anhydride copolymer, Three (2,4- di-tert-butyl-phenyl) phosphite esters, double (2,4- di-tert-butyl-phenyl) pentaerythritol diphosphites, hydroxyl hexichol Stir, will stir in the homogenizer that ketone, hydroxy-phenyl benzotriazole and hydroxyphenyl-triazine are added on main drawing-in device Mix uniform mixture to be added in the main feeding machine of double screw extruder, by tricresyl phosphate, red phosphorus and PolyAd HS Stirred in 02 homogenizer being added on the drawing-in device of 1# sides, the mixture to stir is added into twin-screw squeezes Go out in the 1# sides feeding machine of machine, circular glass fiber, non-circular glass fibre and hollow glass micropearl are added into twin-screw squeezes Go out in the 2# sides feeder of machine, be granulated through double screw extruder, engine speed 400-600r/min, vacuum pressure control exists 0.06-0.08Mpa。
Embodiment 7：
A kind of high abrasion high-temperature resistant nylon 46 composite, is made up of following components in percentage by weight：
33% nylon 46；
18% nylon66 fiber；
4% toughness reinforcing compatilizer (polyethylene octene copolymer elastomer-copolymer-maleic anhydride, polystyrene-ethylene-butylene- Polystyrene-maleic anhydride copolymer, mass ratio 1:3)；
13% halogen-free flame retardants (tricresyl phosphate, red phosphorus, mass ratio 1:1)；
26% glass fibre (circular glass fiber, non-circular glass fibre, mass ratio 2:3)；
0.2% antioxidant (three (2,4- di-tert-butyl-phenyl) phosphite esters, double (2,4- di-tert-butyl-phenyl) pentaerythrites Diphosphites, mass ratio 1:3)；
0.5% anti-UV agent (hydroxy-phenyl benzotriazole, hydroxyphenyl-triazine, mass ratio 1:2),
0.3% heat stabilizer (PolyAd HS 02)；
5% glass microballoon (hollow glass micropearl).
It is nylon 46 resin (moisture 1 ‰) after first drying, nylon 66 resin (moisture 1 ‰), poly- Ethylene octene copolymer elastomer-copolymer-maleic anhydride, polystyrene-ethylene-butylene-polystyrene-maleic anhydride copolymer, Three (2,4- di-tert-butyl-phenyl) phosphite esters, double (2,4- di-tert-butyl-phenyl) pentaerythritol diphosphites, hydroxyphenyl benzene And stirred in the homogenizer that is added on main drawing-in device of triazole and hydroxyphenyl-triazine, the mixture that will be stirred It is added in the main feeding machine of double screw extruder, tricresyl phosphate, red phosphorus and PolyAd HS 02 are added into 1# sides feeds Stirred in homogenizer on material device, the mixture to stir is added to the 1# sides feeding of double screw extruder In machine, circular glass fiber, non-circular glass fibre and hollow glass micropearl are added to the 2# sides feeding of double screw extruder In device, it is granulated through double screw extruder, engine speed 400-600r/min, vacuum pressure is controlled in 0.06-0.08Mpa.
Embodiment 8：
A kind of high abrasion high-temperature resistant nylon 46 composite, is made up of following components in percentage by weight：
30% nylon 46；
17% nylon66 fiber；
5% toughness reinforcing compatilizer (polyethylene octene copolymer elastomer-copolymer-maleic anhydride, ethylene propylene diene rubber-maleic acid Anhydride copolymer, polystyrene-ethylene-butylene-polystyrene-maleic anhydride copolymer, mass ratio 1:1:2)；
13% halogen-free flame retardants (phosphinates, tricresyl phosphate, red phosphorus, mass ratio 1:1:4)；
28% glass fibre (circular glass fiber, non-circular glass fibre, mass ratio 1:1)；
0.3% antioxidant (four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters, double (2,4- bis- uncles Butyl phenyl) pentaerythritol diphosphites, mass ratio 1:3)；
0.4% anti-UV agent is (by histamine, hydroxy-phenyl benzotriazole, hydroxyphenyl-triazine, mass ratio 1:1:3),
0.3% heat stabilizer (PolyAd HS 02)；
6% glass microballoon (hollow glass micropearl).
It is nylon 46 resin (moisture 1 ‰) after first drying, nylon 66 resin (moisture 1 ‰), poly- Ethylene octene copolymer elastomer-copolymer-maleic anhydride, ethylene propylene diene rubber-copolymer-maleic anhydride, polystyrene-ethylene- It is butylene-polystyrene-maleic anhydride copolymer, four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters, double (2,4- di-tert-butyl-phenyl) pentaerythritol diphosphites, it is added to by histamine, hydroxy-phenyl benzotriazole and hydroxyphenyl-triazine Stirred in homogenizer on main drawing-in device, the master that the mixture to stir is added to double screw extruder feeds In material machine, phosphinates, tricresyl phosphate, red phosphorus and PolyAd HS 02 are added to the high-speed stirring on the drawing-in device of 1# sides Mix in machine and stir, the mixture to stir is added in the 1# sides feeding machine of double screw extruder, by circular glass Fiber, non-circular glass fibre and hollow glass micropearl are added in the 2# sides feeder of double screw extruder, are squeezed through twin-screw Go out machine granulation, engine speed 400-600r/min, vacuum pressure is controlled in 0.06-0.08Mpa.
Comparative example 1
The difference of this comparative example and embodiment 1 is, is not added with halogen-free flame retardants and heat stabilizer, by following weight percent The component of ratio is made：
35% nylon 46；
24% nylon66 fiber；
6% toughness reinforcing compatilizer (polyethylene octene copolymer elastomer-copolymer-maleic anhydride, ethylene propylene diene rubber-maleic acid Anhydride copolymer, polystyrene-ethylene-butylene-polystyrene-maleic anhydride copolymer, mass ratio 1:1:1)；
28% glass fibre (circular glass fiber, non-circular glass fibre, mass ratio 1:1)；
0.3% antioxidant (N, N '-hexylidene -1.6- two [(3,5- di-t-butyl -4- hydroxyphenyls) propionamide], four [β - (3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, three (2,4- di-tert-butyl-phenyl) phosphite esters, double (2,4- Di-tert-butyl-phenyl) pentaerythritol diphosphites, mass ratio 1:1:1:1)；
0.7% anti-UV agent is (by histamine, dihydroxy benaophenonel, hydroxy-phenyl benzotriazole, hydroxyphenyl-triazine, mass ratio 1: 1:1:1),
6% glass microballoon (hollow glass micropearl).
It is nylon 46 resin (moisture 1 ‰) after first drying, nylon 66 resin (moisture 1 ‰), poly- Ethylene octene copolymer elastomer-copolymer-maleic anhydride, ethylene propylene diene rubber-copolymer-maleic anhydride, polystyrene-ethylene- Butylene-polystyrene-maleic anhydride copolymer, N, N '-hexylidene -1.6- two [(3,5- di-t-butyl -4- hydroxyphenyls) propionyl Amine], four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters, three (2,4- di-tert-butyl-phenyl) phosphorous acid Ester, double (2,4- di-tert-butyl-phenyl) pentaerythritol diphosphites, by histamine, dihydroxy benaophenonel, hydroxy-phenyl benzotriazole Stirred in the homogenizer being added to hydroxyphenyl-triazine on main drawing-in device, the mixture to stir is added to In the main feeding machine of double screw extruder, circular glass fiber, non-circular glass fibre and hollow glass micropearl are added to double In the 2# sides feeder of screw extruder, it is granulated through double screw extruder, engine speed 400-600r/min, vacuum pressure control In 0.06-0.08Mpa.
Halogen-free flameproof high-temperature resistant nylon 46 composite obtained by above-described embodiment with being obtained in comparative example Composite carry out every test, specific test event is as follows：
Tensile property is tested, and heat distortion temperature, is carried out by ISO75-2；Fire resistance, carried out according to UL-94 standards (1.6mm)；Glow wire test, tested by batten thickness 3mm, test result such as following table：
Test event Heat distortion temperature (DEG C) Fire resistance Glow wire test
Embodiment 1 280 V0 850 DEG C nonflammable
Embodiment 2 276 V0 850 DEG C nonflammable
Embodiment 3 277 V0 850 DEG C nonflammable
Embodiment 4 281 V0 850 DEG C nonflammable
Embodiment 5 281 V0 850 DEG C nonflammable
Embodiment 6 273 V0 850 DEG C nonflammable
Embodiment 7 276 V0 850 DEG C nonflammable
Embodiment 8 278 V0 850 DEG C nonflammable
Comparative example 1 220 V2 850 DEG C of ignitions
The above embodiment of the present invention is only intended to clearly illustrate example of the present invention, and is not to the present invention Embodiment restriction, for those of ordinary skill in the field, can also make on the basis of the above description Other various forms of changes or variation, can not be exhaustive to all embodiments here, every skill for belonging to the present invention The obvious changes or variations that art scheme is extended out still in protection scope of the present invention within.

Claims (10)

  1. A kind of 1. halogen-free flameproof high-temperature resistant nylon 46 composite, it is characterised in that：By following percentage by weight Component is made：
  2. 2. halogen-free flameproof high-temperature resistant nylon 46 composite according to claim 1, it is characterised in that：It is described Toughness reinforcing compatilizer be polyethylene octene copolymer elastomer-copolymer-maleic anhydride, ethylene propylene diene rubber-copolymer-maleic anhydride, Any one in polystyrene-ethylene-butylene-polystyrene-maleic anhydride copolymer or its any a variety of combination.
  3. 3. halogen-free flameproof high-temperature resistant nylon 46 composite according to claim 1, it is characterised in that：It is described Halogen-free flame retardants is any one or its any a variety of combination in phosphinates, tricresyl phosphate, red phosphorus.
  4. 4. halogen-free flameproof high-temperature resistant nylon 46 composite according to claim 1, it is characterised in that：It is described Glass fibre is circular glass fiber, the combination of any one or both in non-circular glass fibre.
  5. 5. halogen-free flameproof high-temperature resistant nylon 46 composite according to claim 1, it is characterised in that：It is described Antioxidant be N, N '-hexylidene -1.6- two [(3,5- di-t-butyl -4- hydroxyphenyls) propionamide], four [β-(3,5- bis- tertiary fourths Base -4- hydroxy phenyls) propionic acid] pentaerythritol ester, three (2,4- di-tert-butyl-phenyl) phosphite esters, double (2,4- di-tert-butyls Base) any one or its any a variety of combination in pentaerythritol diphosphites.
  6. 6. halogen-free flameproof high-temperature resistant nylon 46 composite according to claim 1, it is characterised in that：It is described Anti- UV agent is any a variety of for any one or its in by histamine, dihydroxy benaophenonel, hydroxy-phenyl benzotriazole, hydroxyphenyl-triazine Combination.
  7. 7. halogen-free flameproof high-temperature resistant nylon 46 composite according to claim 1, it is characterised in that：It is described Heat stabilizer be PolyAd HS 02.
  8. 8. halogen-free flameproof high-temperature resistant nylon 46 composite according to claim 1, it is characterised in that：It is described Glass microballoon be hollow glass micropearl.
  9. 9. the preparation side of the halogen-free flameproof high-temperature resistant nylon 46 composite according to claim any one of 1-8 Method, it is characterised in that：It specifically includes following steps：
    Step 1：Nylon 46 and nylon 66 resin are placed in 100 DEG C of baking oven and dry 3-4 hours, makes its aqueous Rate is less than 0.5%；
    Step 2：Nylon 46 resin, nylon 66 resin, toughness reinforcing are weighed respectively by each component percentage by weight in formula Compatilizer, halogen-free flame retardants, glass fibre, antioxidant, anti-UV agent, heat stabilizer and glass microballoon；
    Step 3：Nylon 46 resin, nylon 66 resin, toughness reinforcing compatilizer, antioxidant and anti-UV agent are added at a high speed 2~5min is stirred in mixer, obtains mixture A；Halogen-free flame retardants and heat stabilizer stir mixed in homogenizer 2~5min is closed, obtains mixture B；Glass fibre and glass microballoon are stirred 2~5min in homogenizer, are mixed Compound C；
    Step 4：The draw ratio of double screw extruder needed for production is 40: 1, configures bilateral feeding, and mixture A is fed by main Material is added in double screw extruder, and mixture B and mixture C are added to double screw extruder by two side feedings respectively In, tie rod, pelletizing are extruded after melting mixing and is packed.
  10. 10. the preparation method of halogen-free flameproof high-temperature resistant nylon 46 composite according to claim 9, it is special Sign is：The silicon carbide from charge door to head of the double screw extruder is set as ten sections, and the temperature of first five section is set Determine 280-310 DEG C, rear five section is 270-310, and engine speed 400-600r/min, vacuum pressure control is in 0.06- 0.08MPa。
CN201711143700.6A 2017-11-17 2017-11-17 Halogen-free flameproof high-temperature resistant nylon 46 composite and preparation method thereof Pending CN107778856A (en)

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CN111040440A (en) * 2019-12-26 2020-04-21 广州市聚赛龙工程塑料股份有限公司 Low-density high-wear-resistance nylon composite material and preparation method and application thereof
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CN113265723A (en) * 2021-06-24 2021-08-17 晋江市飞顺郎鞋业有限公司 High-strength anti-aging composite fiber for fly-knitted mesh fabric and preparation method thereof

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Application publication date: 20180309