CN105385133B - Halogen-free flame retardant PC reinforcing material and preparation method thereof and the application in meter case is prepared - Google Patents
Halogen-free flame retardant PC reinforcing material and preparation method thereof and the application in meter case is prepared Download PDFInfo
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Abstract
Application the invention discloses a kind of halogen-free flame retardant PC reinforcing material and preparation method thereof and in meter case is prepared, the material, in terms of 100 parts of parts by weight, it is made up of the raw material of following parts by weight：73 86 parts of makrolon；8 12 parts of glass fibre；26 parts of halogen-free flame-retardant master batch；0.3 1.5 parts of fire retarding synergist；0.2 0.7 parts of anti-dripping agent；0.1 0.5 parts of anti ultraviolet agent；0.05 0.2 parts of light stabilizer；25 parts of stabilisers against hydrolysis；0.3 1 parts of antioxidant；0.2 1 parts of lubricant.The preparation of the halogen-free flame retardant PC reinforcing material, first each component is mixed, obtained again by double screw extruder extruding pelletization, halogen-free flame retardant PC reinforcing material has the characteristics such as high fire-retardance, high durable, cracking resistance, environmental protection, it is highly suitable for preparing meter case, the requirement of the standards of national grid Q/GDW 355 2009 can be met.
Description
Technical field
The present invention relates to glass fiber reinforced polycarbonate material technical field of modification, and in particular to a kind of halogen-free flame retardant PC enhancing
Material and preparation method thereof and the application in meter case is prepared.
Background technology
Shell of the ammeter tank shell as a protectiveness for leading to single household's ammeter metrical instrument in national grid facility
Body, it is required for installing and using in places such as municipal administration, cell, family, rural power grids, factory, enterprise, office, fire-fightings.In recent years, with
The development of national economy, new urbanization carry forward vigorously and the intelligent regeneration of national grid etc., for ammeter box shell
Demand it is very big.
According to the functional characteristic of ammeter box shell and use environment feature, it just needs preferable flame-retarding characteristic and resistance to
Hou Xing.The typically conventional bromide fire retardant progress of traditional fire-retardant polycarbonate (PC) material is fire-retardant, and addition mass fraction 6%~
9% brominated flame-retardant typically can just make PC flame retardant ratings reach UL94V-0 levels, and the addition of bromide fire retardant is for PC's
The influence of every physical and mechanical properties is very small, or even can also increase the impact strength of material to a certain extent.But in practical application
Middle proof, bromide fire retardant heatproof is relatively low, very sensitive for thermal history, and easily imitation frosted glass turns to be yellow at screw rod or cast gate, influences
Products appearance.Especially, substantial amounts of HBr toxic gases can be discharged in the based flame retardant combustion process and more bromines are carcinogenic for oxane class
Material, it is progressively all disabled in developed regions such as West Europe, Japan, North Americas.Simultaneously in terms of weather resistance, bromide fire retardant exists
Because ultraviolet etc. irradiates during use, its C-Br molecular link can occur fracture and produce free radical, and then cause product surface
Jaundice, accelerate the degradation with aging of product.
Ultra-violet absorber can utilize the characteristics of self structure, convert light energy into heat energy, and then avoid macromolecule material
Photooxidation reaction and degradation with aging occur for material.The use environment such as it is exposed to the sun because meter case need to be in outdoor high temperature for a long time, it is made
The service life of product is seriously threatened by problem of aging, and only by ageing-resistant contribution of the addition ultra-violet absorber to PC materials
Act on limited.
For hindered amine light stabilizer as a kind of excellent anti-aging auxiliary agent, it can shield or absorb the energy of ultraviolet,
Quenching singlet oxygen and hydroperoxides are resolved into the functions such as inert matter, make high molecular polymer under the radiation of light,
It can exclude or slow down photochemical reaction possibility, prevent or postpone the process of light aging, it has splendid with ultra-violet absorber
Ageing-resistant cooperative effect.But because hindered amine has alkalescent, PC degraded is easily caused under hot and humid environment, thus
Typically hindered amine as light stabilizer is not added in PC.Analyzed based on more than, two kinds of antiagers is played aging collaboration effect
Should, while it is a problem for being worth research that can avoid its degraded to PC again.
Chinese patent literature CN 103709711A disclose (bulletin) day 2014.04.09, disclose a kind of meter case and use
Halogen-free flame retardant PC/GF composites, constituent is in parts by mass：PC75-90, glass 8-15, toughener 2-4, coupling agent
0.3-0.5, antioxidant 0.1-0.3, halogen-free flame retardants 1-3, anti-dripping agent 0.1-0.4, compound floating fine remover 0.8-1.2.System
Standby material has HI high impact, high intensity, high flame retardant and the feature of environmental protection, is widely used on meter case.But the technology is not examined
The use environment for considering meter case determines that it needs very harsh ageing-resistant performance, and otherwise its shorter service life will
Cause very serious safety problem.Meanwhile its toughening agent contains methylmethacrylate polymer, does not meet national grid
The requirement of meter case Q/GDW 355-2009 standards.
Chinese patent literature CN 104592732A disclose (bulletin) day 2015.05.06, disclose a kind of low addition Halogen
Fire-retardant enhancing PC formula and production method, it, which is formulated composition, includes the composition of following mass fraction：PC70-80 parts, Halogen resistance
Fire agent 10-15 parts, glass fibre 15-20 parts, antioxidant 0.1-0.5 parts, transparent talcum powder 5-10 parts, lubricant 0.1-1 parts, idol
Join agent 0.1-0.5 parts, anti-floating fibre agent 0.1-1.0 parts, anti-dripping agent 0.1-1.0 parts, other processing aids 0.5-0.8 parts.The hair
The color of the material of bright preparation is good, temperature tolerance is high, good flame resistance, can be used for the electronics such as electronic apparatus, meter case, connector
Product.The technology does not also consider the ageing properties of material simultaneously, while the addition of its halogen-free flame retardants is very high, will certainly be to material
Every physical and mechanical property of material brings larger destruction.Talcum powder is added in the invention, does not meet outside national grid ammeter
The requirement of shell Q/GDW 355-2009 standards.
Chinese patent literature CN 104140662A disclose (bulletin) day 2014.11.12, disclose a kind of enhancing fire retardation PC
Base resin special material and preparation method thereof, it is made up of the raw material of following mass parts：The PC particles, the PC of 2-5 parts of 62-84 parts
Powder, the glass fibre of 10-30 parts, the fire retardant of 1.15-5 parts, the antioxidant of 0.016-0.02 parts, the anti-floating of 0-0.005 parts are fine
Agent, the anti ultraviolet agent of 0.008-0.012 parts.Material prepared by the invention is in fire-retardant reachable the V0 levels of 1.6mm, in UVB irradiations 1000h
The yellowness index value added of material is smaller afterwards, available for the meter case product in electronic instrument industry.Though the technology is considered
The weatherable problem of material, corresponding modification is done to the weather resistance of material, but aging effect is general.Meanwhile the technology
Although the bromide fire retardant of selection influences very little to material property, not environmentally, although and the N systems selected or P flame retardant rings
Guarantor's type is preferable, but its flame retarding efficiency is low, and 10-20 DEG C can be reduced simultaneously for the heat distortion temperature of PC materials, causes the electricity of injection
The temperature in use of watch case is relatively low.
The content of the invention
Object of the present invention is to provide a kind of halogen-free flame retardant PC reinforcing material and preparation method thereof and preparing ammeter
Application in shell, the halogen-free flame retardant PC reinforcing material have the characteristics such as high fire-retardance, high durable, cracking resistance, environmental protection, can meet state
Family's power network Q/GDW 355-2009 standards requirement.
To achieve the above object, the technical solution adopted by the present invention is as follows：
A kind of halogen-free flame retardant PC reinforcing material, in terms of 100 parts of parts by weight, it is made up of the raw material of following parts by weight：
In the present invention, combined by the specific components of certain content, each component is mixed, can interacted, and is produced
Raw synergy, while properties are assigned, ensures excellent mechanical property so that halogen-free flame retardant PC enhancing of the invention
Material has the characteristics such as high fire-retardance, high durable, cracking resistance, environmental protection, is highly suitable for production of intelligent meter case, can meet state
Family's power network Q/GDW 355-2009 standards requirement.
Preferably, described halogen-free flame retardant PC reinforcing material, in terms of 100 parts of parts by weight, by the raw material of following parts by weight
It is made：
Melt flow rate (MFR) of the described makrolon under the conditions of 300 DEG C, 1.2Kg is 5~10g/10min, is divided equally again
Son amount is 3.0 ten thousand~4.0 ten thousand.Because sulfonate halogen-free flame retardants does not have flame retardant effect to toughener, therefore, the system should not add
Add toughener, can ensure the excellent toughness of material from the PC resin of macromolecule.
Described glass fibre is surface treated alkali-free short glass fiber, and Length of Glass Fiber is 2.0~4mm, glass
Fine 8-15 μm of diameter, further preferably, Length of Glass Fiber 3.0mm, 10-13 μm of glass diameter.Glass fibre can specifically use deep
The alkali-free short glass fiber of Xian Gu Science and Technology Ltd.s of ditch between fields city production, it is by passing through silane coupler and special infiltration agent prescription
The long fibre of processing is chopped and formed, Length of Glass Fiber 3.0mm, 10-13 μm of glass diameter.
Described halogen-free flame-retardant master batch is mixed by halogen-free flame retardants and makrolon, and described halogen-free flame retardants is sulphur
Hydrochlorate fire retardant, the amount of described halogen-free flame retardants account for the 5~15% of halogen-free flame-retardant master batch gross mass.Described sulfonate is fire-retardant
Agent can specifically use sulfonate salt flame HES-FR (SLOSS companies of the U.S.) or trichlorine benzene sulfonic acid sodium salt STB, and (U.S. SLOSS is public
Department, F-531) in any one.
Described fire retarding synergist is silicon-series five-retardant, and silicon-series five-retardant can specifically use the model of Dow Corning Corporation's production
Model KR480 (the ShinEtsu of product or the production of Japanese chemical company of SHIN-ETSU HANTOTAI for FAC-107 (Dow Corning)
Chemical product).
Described anti-dripping agent is SAN cladded type anti-dripping agents, and SAN cladded types anti-dripping agent can use SAN cladding PTFE,
That is SAN resin-coatings polytetrafluoroethylene (PTFE), FS-200 (HANNANOFS-200) product is such as received using South Korea's Chinese, SAN encasement
Impart the good dispersion effects of PTFE.
Described anti ultraviolet agent is benzophenone anti ultraviolet agent, one or both of benzotriazole anti ultraviolet agent,
2-hydroxy-4-n-octoxybenzophenone (UV-531), 2- hydroxyl -4- methoxyl group hexichol can be selected in benzophenone anti ultraviolet agent
One or both of ketone (UV-9), benzotriazole anti ultraviolet agent select 2- (the 2 ˊ-ˊ of hydroxyl-5-aminomethyl phenyl) benzo three
Nitrogen azoles (UV-P), 2'- (the 2'- hydroxyl -3'- tert-butyl group -5'- aminomethyl phenyls) -5- chlorobenzotriazoles (UV-326), 2- (2 '-hydroxyls
Base -3 ', 5 '-di-tert-butyl-phenyl) -5- chlorobenzotriazoles (UV-327), 2- (2'- hydroxyls -5'- (1,1,3,3- tetramethyl fourths
Base) phenyl) BTA (UV-329), 2- (2'- hydroxyls -3', 5' double (a, a- dimethyl benzyl) phenyl) BTA (UV-
One or both of 234) more than (including two kinds).
Described light stabilizer (is obstructed for the polymer of succinic acid and (4- hydroxyl -2,2,6,6- tetramethyl -1- piperidine alcohols)
Amine light stabilizer 622) or N, N '-bis--(2,2,6,6- tetramethyl -4- piperidyls) -1,6- hexamethylene diamines and 2,4,6- tri- chloro- 1,3,
The polymer of 5- triazines and 1, the reaction product (hindered amine as light stabilizer 944) of 1,3,3- tetramethyl butylamine, is aggretion type height
Molecular weight hindered amine light stabilizer.
Described stabilisers against hydrolysis is epoxy family macromolecule hydrolysis-resisting agent, the functional polymer SAG-005 of response type, i.e.,
Specifically from the good stabilisers against hydrolysis for easily holding SAG-005, the good stabilisers against hydrolysis for easily holding SAG-005 is styrene-propene
Nitrile-glycidyl methacrylate copolymer.Contain active epoxy functional group on the stabilisers against hydrolysis strand, it can be with
Terminal hydroxy group reaction on makrolon strand, so suppress makrolon occur ester exchange reaction under the conditions of hot and humid and
Accelerated degradation, degraded catalysis caused by makrolon is made under high humidity environment so as to greatly suppress hindered amine as light stabilizer
With.
Described antioxidant is the compound of antioxidant 1076 and irgasfos 168, and its part by weight is 1:1.
Described lubricant be calcium stearate, pentaerythritol stearate (PETS), one or both of silicone powder with
On.
Most preferably, described halogen-free flame retardant PC reinforcing material, in terms of 100 parts of parts by weight, by the raw material of following parts by weight
It is made：
Described anti ultraviolet agent is benzophenone anti ultraviolet agent, one or both of benzotriazole anti ultraviolet agent,
Benzophenone anti ultraviolet agent is 2-hydroxy-4-n-octoxybenzophenone (UV-531), ESCALOL 567
One or both of (UV-9), benzotriazole anti ultraviolet agent is 2- (the 2 ˊ-ˊ of hydroxyl-5-aminomethyl phenyl) BTA
(UV-P), 2'- (the 2'- hydroxyl -3'- tert-butyl group -5'- aminomethyl phenyls) -5- chlorobenzotriazoles (UV-326), 2- (2 '-hydroxyl -3 ',
5 '-di-tert-butyl-phenyl) -5- chlorobenzotriazoles (UV-327), 2- (2'- hydroxyls -5'- (1,1,3,3- tetramethyl butyls) phenyl)
In BTA (UV-329), 2- (double (a, the a- dimethyl benzyl) phenyl of 2'- hydroxyls -3', 5') BTA (UV-234)
One or more kinds of (including two kinds)；
Described light stabilizer (is obstructed for the polymer of succinic acid and (4- hydroxyl -2,2,6,6- tetramethyl -1- piperidine alcohols)
Amine light stabilizer 622) or N, N '-bis--(2,2,6,6- tetramethyl -4- piperidyls) -1,6- hexamethylene diamines and 2,4,6- tri- chloro- 1,3,
The polymer of 5- triazines and the reaction product (hindered amine as light stabilizer 944) of 1,1,3,3- tetramethyl butylamine；
Described stabilisers against hydrolysis is using the good stabilisers against hydrolysis for easily holding SAG-005.
A kind of preparation method of halogen-free flame retardant PC reinforcing material, comprises the following steps：
1) by makrolon, halogen-free flame-retardant master batch, fire retarding synergist, anti-dripping agent, anti ultraviolet agent, light stabilizer, water resistant
It is uniform to solve stabilizer, antioxidant and mix lubricant, obtains mixed material；
2) mixed material obtained by step 1) is fed by the main spout of double screw extruder, glass fibre is from double spiral shells
The side spout of bar extruder adds, and extruded, granulation, produces halogen-free flame retardant PC reinforcing material after drying.
Preferably, in step 1), makrolon, halogen-free flame-retardant master batch, fire retarding synergist, anti ultraviolet agent, light is stable
Agent, stabilisers against hydrolysis, antioxidant and lubricant are added in mixed at high speed mixer, and first 500~1500rpm stirrings 1~
After 5min, then 1000~2000rpm stirs 2~8min, adds 100~300rpm of anti-dripping agent low speed and stirs 0.2~2min,
Obtain mixed material.
Preferably, in step 2), described double screw extruder extrudes the temperature setting for each warm area that discharges from being fed to
For：One area：245~255 DEG C, 2nd area：260~270 DEG C, 3rd area：270~280 DEG C, 4th area：270~280 DEG C, 5th area：285~
295 DEG C, 6th area：255~265 DEG C, 7th area：245~255 DEG C, 8th area：235~245 DEG C, 9th area：235~245 DEG C, die head：
255~265 DEG C, the screw speed of described double screw extruder is 600~800rpm.High screw speed can produce stronger
Dispersion effect, be relatively beneficial to the scattered of halogen-free flame retardants, and then improve its flame retardant effect.
Halogen-free flame retardant PC reinforcing material prepared by the present invention has the characteristics such as high fire-retardance, high durable, cracking resistance, environmental protection, specially
For high request intelligent electric meter shell develop, be highly suitable for preparing meter case, national grid can be met for ammeter outside
The all technical requirement of shell material.
Compared with prior art, the present invention is advantageous in that：
Special halogen-free flame retardant PC reinforcing material of meter case of the present invention and preparation method thereof, the material uses sulfonate Halogen
Fire retardant and the mode of silicon systems fire retarding synergist compounding can obtain good flame retardant effect, and fire retardant addition is few, have economy
Environmental protection characteristic.Using the technique of the high screw speed of fire-retardant master granule and double screw extruder, halogen-free flameproof can be more beneficial for
Agent disperses, and then reduces the addition of fire retardant and improve flame retarding efficiency.
The alkalescent of hindered amine as light stabilizer is easily caused the degraded of PC materials, therefore general it is not recommended that addition is in PC materials
In.But light stabilizer is fabulous antiager again, especially with ultra-violet absorber compounding use, both not same-actions
Good ageing-resistant synergistic effect can be played between mechanism.For high molecular polymer under the radiation of light, light stabilizer can decompose hydrogen
Peroxide, excited oxygen ion is quenched, captures free radical；And ultra-violet absorber can convert light energy into heat energy, avoid
Photooxidation reaction occurs for high polymer material, and both can play good synergistic effect by the different mechanism of action, and then prevent
Or the process of delay light aging, so as to reach the purpose for extending high polymer product service life.The present invention passes through addition
Stabilisers against hydrolysis SAG-005 with unique activity epoxy-functional, it can be anti-with the terminal hydroxy group on makrolon strand
Should, and then suppress makrolon and occur ester exchange reaction under the conditions of hot and humid and accelerated degradation, so as to greatly suppress by
Amine light stabilizer is hindered under high humidity environment to catalytic action of being degraded caused by makrolon.The present invention passes through the specific of certain content
Component is combined, and each component is mixed, can interacted, and produces synergy, while properties are assigned, is ensured
Excellent mechanical property so that halogen-free flame retardant PC reinforcing material of the invention has high fire-retardance, high durable, cracking resistance, environmental protection etc.
Characteristic, production of intelligent meter case is highly suitable for, the requirement of national grid Q/GDW355-2009 standards can be met.
Embodiment
The present invention is specifically described below by embodiment, but the technical scope of the present invention is not limited to these implementations
Example.In the present invention, in the case of not specified, part refers both to parts by weight.
In the embodiment of the present invention, specifically from the raw material of following brand：
Makrolon uses the Bayer Bitterfeld GmbH trade mark as 2805 product, the melt flows speed under the conditions of 300 DEG C, 1.2Kg
Rate is 10g/10min, and weight average molecular weight is 3.5 ten thousand.
Glass fibre uses the alkali-free short glass fiber of Xian Gu Science and Technology Ltd.s of Shenzhen production, is by by silane
Coupling agent and the long fibre of special infiltration agent prescription processing are chopped and formed, Length of Glass Fiber 3.0mm, 10-13 μm of glass diameter.
Halogen-free flame-retardant master batch is mixed by halogen-free flame retardants and makrolon (the Bayer Bitterfeld GmbH trade mark is 2805), Halogen resistance
Combustion agent is sulfonate salt flame HES-FR (SLOSS companies of the U.S., FR500) or trichlorine benzene sulfonic acid sodium salt STB (U.S. SLOSS public affairs
Department, F-531) in any one, halogen-free flame retardants be halogen-free flame-retardant master batch gross mass 10%.Halogen-free flame retardants uses sulfonic acid
During salt fire retardant HES-FR (SLOSS companies of the U.S., FR500), HES halogen-free flame-retardant master batchs are obtained.Halogen-free flame retardants uses trichlorine
During benzene sulfonic acid sodium salt STB (SLOSS companies of the U.S., F-531), STB halogen-free flame-retardant master batchs are obtained.
Fire retarding synergist is silicon-series five-retardant, and silicon-series five-retardant is specifically using the model FAC- of Dow Corning Corporation's production
107 (Dow Corning) product or the model KR480 (ShinEtsu Chemical) of Japanese chemical company of SHIN-ETSU HANTOTAI production
Product.
Anti-dripping agent is SAN cladded type anti-dripping agents, coats PTFE using SAN, FS-200 is received using South Korea's Chinese
(HANNANOFS-200) product.
Anti ultraviolet agent is benzophenone anti ultraviolet agent, one or both of benzotriazole anti ultraviolet agent, hexichol first
For ketone anti ultraviolet agent from one or both of UV-531, UV-9, benzotriazole anti ultraviolet agent selects benzotriazole UV-
P, one kind in benzotriazole UV-326, benzotriazole UV-327, benzotriazole UV-329, benzotriazole UV-234
Or two or more (including two kinds).
Light stabilizer is hindered amine as light stabilizer 622 or hindered amine as light stabilizer 944.
Stabilisers against hydrolysis easily holds SAG-005 stabilisers against hydrolysis from good.
Antioxidant is the compound of antioxidant 1076 and irgasfos 168, and its part by weight is 1:1.
Lubricant is more than one or both of calcium stearate, pentaerythritol stearate (PETS), silicone powder.
Embodiment 1
The present embodiment is raw materials used and mass percent is：Makrolon 85.95%, alkali-free glass fiber 8%, the resistance of HES Halogens
Fire master batch 2%, fire retarding synergist KR480 0.3%, anti-dripping agent 0.5%, anti ultraviolet agent UV-531 0.2%, light stabilizer
622 0.05%, stabilisers against hydrolysis SAG-005 2%, antioxidant 0.5%, lubricant stearic acid calcium 0.5%.
The preparation method of the present embodiment is specific as follows：By above-mentioned makrolon, halogen-free flame-retardant master batch, fire retarding synergist, anti-
Ultraviolet dose, light stabilizer, stabilisers against hydrolysis, antioxidant and lubricant are added in mixed at high speed mixer, and first 1000rpm is stirred
After mixing 3min, 1500rpm stirring 5min, anti-dripping agent low speed 200rpm stirring 0.5min are added, obtain mixed material.Then
Said mixture material is added in double screw extruder, glass is fed from side feeding, is granulated to obtain intelligent electric meter through melting extrusion
The special halogen-free flame retardant PC reinforcing material of shell.Double screw extruder used extrudes the temperature setting for each warm area that discharges from being fed to
For：One area：250 DEG C, 2nd area：265 DEG C, 3rd area：265 DEG C, 4th area：265 DEG C, 5th area：280 DEG C, 6th area：260 DEG C, 7th area：250
DEG C, 8th area：240 DEG C, 9th area：240 DEG C, die head：260 DEG C, the screw speed of described double screw extruder is 800rpm.
Embodiment 2
The present embodiment is raw materials used and mass percent is：Makrolon 81%, alkali-free glass fiber 8%, HES halogen-free flameproofs are female
Grain 5%, fire retarding synergist KR480 1%, anti-dripping agent 0.5%, anti ultraviolet agent UV-531 0.4%, light stabilizer 622
0.1%th, stabilisers against hydrolysis SAG-005 3%, antioxidant 0.4%, lubricant stearic acid calcium 0.6%.
The preparation method of the present embodiment is specific as follows：Added after above-mentioned each constituent is well mixed according to embodiment 1
Into double screw extruder, it is granulated to obtain the special halogen-free flame retardant PC reinforcing material of intelligent electric meter shell through melting extrusion.It is used double
Screw extruder working process parameter is same as Example 1.
Embodiment 3
The present embodiment is raw materials used and mass percent is：Makrolon 80%, alkali-free glass fiber 8%, HES halogen-free flameproofs are female
Grain 5%, fire retarding synergist KR480 1%, anti-dripping agent 0.5%, anti ultraviolet agent UV-531 0.4%, light stabilizer 622
0.1%th, stabilisers against hydrolysis SAG-005 4%, antioxidant 0.4%, lubricant stearic acid calcium 0.6%.
The preparation method of the present embodiment is specific as follows：Added after above-mentioned each constituent is well mixed according to embodiment 1
Into double screw extruder, it is granulated to obtain the special halogen-free flame retardant PC reinforcing material of intelligent electric meter shell through melting extrusion.Twin-screw
Extruder screw rotating speed is set to 600rpm, and other working process parameters of double screw extruder used are same as Example 1.
Embodiment 4
The present embodiment is raw materials used and mass percent is：Makrolon 76.9%, alkali-free glass fiber 10%, the resistance of HES Halogens
Fire master batch 5%, fire retarding synergist FAC-107 1%, anti-dripping agent 0.6%, anti ultraviolet agent UV-P 0.3%, light stabilizer 944
0.2%th, stabilisers against hydrolysis SAG-005 5%, antioxidant 0.8%, lubricant PETS 0.2%.
The preparation method of the present embodiment is specific as follows：Added after above-mentioned each constituent is well mixed according to embodiment 1
Into double screw extruder, it is granulated to obtain the special halogen-free flame retardant PC reinforcing material of intelligent electric meter shell through melting extrusion.It is used double
Screw extruder working process parameter is same as Example 1.
Embodiment 5
The present embodiment is raw materials used and mass percent is：Makrolon 81.2%, alkali-free glass fiber 10%, the resistance of HES Halogens
Fire that master batch 3%, fire retarding synergist FAC-107 1%, anti-dripping agent 0.3%, anti ultraviolet agent UV-531 and UV-P be each 0.2%, light
Stabilizer 622 0.1%, stabilisers against hydrolysis SAG-005 3%, antioxidant 0.4%, lubricant silicone powder 0.6%.
The preparation method of the present embodiment is specific as follows：Added after above-mentioned each constituent is well mixed according to embodiment 1
Into double screw extruder, it is granulated to obtain the special halogen-free flame retardant PC reinforcing material of intelligent electric meter shell through melting extrusion.It is used double
Screw extruder working process parameter is same as Example 1.
Embodiment 6
The present embodiment is raw materials used and mass percent is：Makrolon 83%, alkali-free glass fiber 8%, HES halogen-free flameproofs are female
Grain 3.5%, fire retarding synergist KR480 0.5%, anti-dripping agent 0.5%, anti ultraviolet agent UV-531 and UV-329 are each 0.2%, light
Stabilizer 622 0.1%, stabilisers against hydrolysis SAG-005 3%, antioxidant 0.3%, lubricant silicone powder 0.7%.
The preparation method of the present embodiment is specific as follows：Added after above-mentioned each constituent is well mixed according to embodiment 1
Into double screw extruder, it is granulated to obtain the special halogen-free flame retardant PC reinforcing material of intelligent electric meter shell through melting extrusion.It is used double
Screw extruder working process parameter is same as Example 1.
Embodiment 7
The present embodiment is raw materials used and mass percent is：Makrolon 81.95%, alkali-free glass fiber 12%, the resistance of STB Halogens
Fire master batch 2%, fire retarding synergist KR480 0.3%, anti-dripping agent 0.5%, anti ultraviolet agent UV-9 0.2%, light stabilizer 944
0.05%th, stabilisers against hydrolysis SAG-005 2%, antioxidant 0.5%, lubricant PETS 0.5%.
The preparation method of the present embodiment is specific as follows：Added after above-mentioned each constituent is well mixed according to embodiment 1
Into double screw extruder, it is granulated to obtain the special halogen-free flame retardant PC reinforcing material of intelligent electric meter shell through melting extrusion.It is used double
Screw extruder working process parameter is same as Example 1.
Embodiment 8
The present embodiment is raw materials used and mass percent is：Makrolon 83%, alkali-free glass fiber 8%, STB halogen-free flameproofs are female
Grain 3.5%, fire retarding synergist KR480 0.5%, anti-dripping agent 0.5%, anti ultraviolet agent UV-531 and UV-326 are each 0.2%, light
Stabilizer 622 0.1%, stabilisers against hydrolysis SAG-005 3%, antioxidant 0.3%, lubricant stearic acid calcium 0.7%.
The preparation method of the present embodiment is specific as follows：Added after above-mentioned each constituent is well mixed according to embodiment 1
Into double screw extruder, it is granulated to obtain the special halogen-free flame retardant PC reinforcing material of intelligent electric meter shell through melting extrusion.It is used double
Screw extruder working process parameter is same as Example 1.
Embodiment 9
The present embodiment is raw materials used and mass percent is：Makrolon 77.8%, alkali-free glass fiber 10%, the resistance of STB Halogens
Fire master batch 4%, fire retarding synergist FAC-107 1%, anti-dripping agent 0.5%, anti ultraviolet agent UV-9 0.3%, UV-234
0.2%th, light stabilizer 622 0.2%, stabilisers against hydrolysis SAG-005 5%, antioxidant 0.5%, lubricant PETS 0.5%.
The preparation method of the present embodiment is specific as follows：Added after above-mentioned each constituent is well mixed according to embodiment 1
Into double screw extruder, it is granulated to obtain the special halogen-free flame retardant PC reinforcing material of intelligent electric meter shell through melting extrusion.It is used double
Screw extruder working process parameter is same as Example 1.
Embodiment 10
The present embodiment is raw materials used and mass percent is：Makrolon 77.3%, alkali-free glass fiber 10%, the resistance of STB Halogens
Fire master batch 5%, fire retarding synergist KR480 0.5%, anti-dripping agent 0.5%, anti ultraviolet agent UV-531 0.2%, UV-P
0.15%th, UV-329 0.15%, light stabilizer 944 0.2%, stabilisers against hydrolysis SAG-005 5%, antioxidant 0.5%, profit
Lubrication prescription PETS 0.5%.
The preparation method of the present embodiment is specific as follows：Added after above-mentioned each constituent is well mixed according to embodiment 1
Into double screw extruder, it is granulated to obtain the special halogen-free flame retardant PC reinforcing material of intelligent electric meter shell through melting extrusion.It is used double
Screw extruder working process parameter is same as Example 1.
Testing method：
Physical and mechanical property：Tensile property test is with reference to GB/T1040.2-2006 standards；Elongation at break tests reference
GB/T1040.2-2006 standards, rate of extension 5mm/min；Stretch modulus test is drawn with reference to GB/T1040.2-2006 standards
It is 1mm/min to stretch speed；With reference to GB/T9341-2008 standards, Bending Deformation speed is 5mm/min for bending property test；Bending
For modulus test with reference to GB/T9341-2008 standards, Bending Deformation speed is 2mm/min；Impact property test is with reference to GB/
T1043.1-2008 standards；Heat distortion temperature (1.82Mpa) is with reference to GB/T1634.2-2004 standards.
Fire resistance：Vertical combustion is with reference to GB/T2408-2008 standards.
Weather resistance：The material of preparation is molded (injection temperature on injection machine：265 DEG C, 260 DEG C, 260 DEG C, 250 DEG C) into
Colour table thick 2.0mm, is then put in ultraviolet ageing case and is tested, and is reached and is taken out colour table respectively after 1500h and 2000h and test it
L, a, b colour, then contrasted with L, a, b original value, calculate aging aberration △ E
The special halogen-free flame retardant PC reinforcing material of intelligent electric meter shell prepared by embodiment 1~10 is pressed into above-mentioned experimental test side
Method is tested, and its properties data is as shown in table 1 below.
Table 1
Continued 1
From above table as can be seen that the preferably suitable halogen-free flame retardants of the present invention and silicon systems synergist, preferably properly
Extrusion processing technology, obtain fabulous fire resistance halogen-free flameproof enhancing PC materials；It is by embodiment it can be found that high
Extruder screw rotating speed, advantageously in the scattered of halogen-free flame retardants, it can make material obtain outstanding fire resistance.Together
When, pass through ultraviolet absorber and hindered amine as light stabilizer and compound so that this is material modified to have splendid weatherability.The modification material
Material can be used for injection intelligent electric meter shell, can fully meet the associated specifications of national grid.
Comparative example 1
This comparative example is raw materials used and mass percent is：Makrolon 77.3%, alkali-free glass fiber 10%, the resistance of STB Halogens
Fire master batch 5%, fire retarding synergist KR480 0.5%, anti-dripping agent 0.5%, anti ultraviolet agent UV-531 0.3%, UV-P
0.2%th, UV-329 0.2%, stabilisers against hydrolysis SAG-005 5%, antioxidant 0.5%, lubricant PETS 0.5%.
The preparation method of this comparative example is specific as follows：Added after above-mentioned each constituent is well mixed according to embodiment 1
Into double screw extruder, it is granulated to obtain the special halogen-free flame retardant PC reinforcing material of intelligent electric meter shell through melting extrusion.It is used double
Screw extruder working process parameter is same as Example 1.
Comparative example 2
This comparative example is raw materials used and mass percent is：Makrolon 77%, alkali-free glass fiber 10%, STB halogen-free flameproofs
Master batch 5%, fire retarding synergist KR480 0.5%, anti-dripping agent 0.5%, light stabilizer 944 0.7%, stabilisers against hydrolysis
SAG-005 5%, antioxidant 0.5%, lubricant PETS 0.5%.
The preparation method of this comparative example is specific as follows：Added after above-mentioned each constituent is well mixed according to embodiment 1
Into double screw extruder, it is granulated to obtain the special halogen-free flame retardant PC reinforcing material of intelligent electric meter shell through melting extrusion.It is used double
Screw extruder working process parameter is same as Example 1.
Comparative example 3
This comparative example is raw materials used and mass percent is：Makrolon 82%, alkali-free glass fiber 10%, STB halogen-free flameproofs
Master batch 5%, fire retarding synergist KR480 0.5%, anti-dripping agent 0.5%, anti ultraviolet agent UV-531 0.2%, UV-P 0.15%,
UV-329 0.15%, light stabilizer 944 0.2%, antioxidant 0.5%, lubricant PETS 0.5%.
The preparation method of this comparative example is specific as follows：Added after above-mentioned each constituent is well mixed according to embodiment 1
Into double screw extruder, it is granulated to obtain the special halogen-free flame retardant PC reinforcing material of intelligent electric meter shell through melting extrusion.It is used double
Screw extruder working process parameter is same as Example 1.
The special halogen-free flame retardant PC reinforcing material of intelligent electric meter shell prepared by comparative example 1~3 is pressed into above-mentioned experimental test side
Method is tested, and its properties data is as shown in table 2 below.
Table 2
* "-" represents sample aging broken, can not test aging aberration.
The purpose of above comparative example mainly studies hindered amine as light stabilizer with ultraviolet absorber for the old of the material
Change the influence of performance, and the stabilisers against hydrolysis SAG-005 containing active epoxy functional group for suppressing hindered amine light stabilizer
Agent is under high humidity environment to catalytic action of being degraded caused by makrolon.Contrast above table data and embodiment 10 can be seen
Go out, ultraviolet absorber or light stabilizer individually added compared to comparative example 1-2, embodiment 10 using ultraviolet absorber with by
The stable compounding of amine light is hindered, generates good ageing-resistant synergistic effect between the two, ageing-resistant performance is obviously improved.
From the experimental data of comparative example 3 can be seen that the stabilisers against hydrolysis SAG-005 with epoxy-reactive functional group by with poly- carbon
Terminal hydroxy group reaction on acid ester molecules chain, greatly inhibits alkalescent hindered amine as light stabilizer under hot and humid environment to poly-
Degraded catalytic action caused by carbonic ester.
Claims (6)
- A kind of 1. application of halogen-free flame retardant PC reinforcing material in meter case is prepared, it is characterised in that described halogen-free flameproof PC reinforcing materials are made up in terms of 100 parts of parts by weight of the raw material of following parts by weight：Described halogen-free flame-retardant master batch is mixed by halogen-free flame retardants and makrolon, and described halogen-free flame retardants is sulfonate Fire retardant, the amount of described halogen-free flame retardants account for the 5~15% of halogen-free flame-retardant master batch gross mass；Described fire retarding synergist is silicon-series five-retardant；Described stabilisers against hydrolysis is epoxy family macromolecule hydrolysis-resisting agent.
- 2. application according to claim 1, it is characterised in that described makrolon is under the conditions of 300 DEG C, 1.2Kg Melt flow rate (MFR) is 5~10g/10min, and weight average molecular weight is 3.0 ten thousand~4.0 ten thousand；Described glass fibre is surface treated alkali-free short glass fiber, and Length of Glass Fiber is 2.0~4mm, and glass is straight 8-15 μm of footpath.
- 3. application according to claim 1, it is characterised in that described anti ultraviolet agent be benzophenone anti ultraviolet agent, One or both of benzotriazole anti ultraviolet agent, benzophenone anti ultraviolet agent use 2- hydroxyl -4- n-octyloxy hexichol One or both of ketone, ESCALOL 567, benzotriazole anti ultraviolet agent use 2- (2 ˊ-hydroxyl -5 ˊ-aminomethyl phenyl) BTA, 2'- (the 2'- hydroxyl -3'- tert-butyl group -5'- aminomethyl phenyls) -5- chlorobenzotriazoles, 2- (2 ' - Hydroxyl -3 ', 5 '-di-tert-butyl-phenyl) -5- chlorobenzotriazoles, 2- (2'- hydroxyls -5'- (1,1,3,3- tetramethyl butyls) phenyl) It is more than one or both of BTA, 2- (double (a, the a- dimethyl benzyl) phenyl of 2'- hydroxyls -3', 5') BTA.
- 4. application according to claim 1, it is characterised in that described light stabilizer be hindered amine as light stabilizer 622 or Hindered amine as light stabilizer 944.
- 5. application according to claim 1, it is characterised in that the preparation method bag of described halogen-free flame retardant PC reinforcing material Include following steps：1) it is makrolon, halogen-free flame-retardant master batch, fire retarding synergist, anti-dripping agent, anti ultraviolet agent, light stabilizer, resistant to hydrolysis is steady It is uniform to determine agent, antioxidant and mix lubricant, obtains mixed material；2) mixed material obtained by step 1) is fed by the main spout of double screw extruder, glass fibre squeezes from twin-screw The side spout for going out machine adds, and extruded, granulation, produces halogen-free flame retardant PC reinforcing material after drying.
- 6. application according to claim 5, it is characterised in that in step 1), by makrolon, halogen-free flame-retardant master batch, resistance Combustion synergist, anti ultraviolet agent, light stabilizer, stabilisers against hydrolysis, antioxidant and lubricant are added in mixed at high speed mixer, After first 500~1500rpm stirs 1~5min, then 1000~2000rpm stirs 2~8min, adds anti-dripping agent low speed 100 ~300rpm stirs 0.2~2min, obtains mixed material；In step 2), described double screw extruder is from the discharge temperature setting of each warm area of extrusion is fed to：One area：245~ 255 DEG C, 2nd area：260~270 DEG C, 3rd area：270~280 DEG C, 4th area：270~280 DEG C, 5th area：285~295 DEG C, 6th area： 255~265 DEG C, 7th area：245~255 DEG C, 8th area：235~245 DEG C, 9th area：235~245 DEG C, die head：255~265 DEG C, institute The screw speed for the double screw extruder stated is 600~800rpm.
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| CN106009583A (en) * | 2016-05-24 | 2016-10-12 | 深圳市富恒新材料股份有限公司 | Sulfonate flame-retardant PC (polycarbonate) engineering plastic and preparation method thereof |
| CN106497000A (en) * | 2016-12-06 | 2017-03-15 | 佛山市高明区生产力促进中心 | A kind of polycarbonate compositions with anti-flaming function |
| CN108017894B (en) * | 2017-11-29 | 2020-04-17 | 合肥圆融新材料有限公司 | High-low temperature resistant hydrolysis-resistant PC alloy and preparation method thereof |
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| CN109021534B (en) * | 2018-07-19 | 2020-11-10 | 中广核俊尔新材料有限公司 | High-temperature and high-humidity resistant polycarbonate composition and preparation method thereof |
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| CN110066504B (en) * | 2019-04-03 | 2020-10-23 | 广东聚石化学股份有限公司 | Low-odor flame-retardant PC/PBT alloy and preparation method thereof |
| TWI773925B (en) * | 2019-09-18 | 2022-08-11 | 大陸商漢達精密電子（昆山）有限公司 | High performance halogen free flame retardant pc/gf composite material and product thereof |
| CN111548620B (en) * | 2020-05-06 | 2022-08-16 | 宁波浙铁大风化工有限公司 | Environment-friendly optical-grade polycarbonate and preparation method thereof |
| CN113801452B (en) * | 2020-06-12 | 2023-09-12 | 汉达精密电子(昆山)有限公司 | High-performance glass fiber reinforced PC material and product thereof |
| CN115449207B (en) * | 2022-09-21 | 2024-02-23 | 中车青岛四方机车车辆股份有限公司 | Halogen-free flame-retardant reinforced PC composite material and preparation method and application thereof |
| CN115505252A (en) * | 2022-10-17 | 2022-12-23 | 苏州耐特福材料科技有限公司 | High-toughness high-modulus flame-retardant reinforced PC material and preparation method thereof |
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