CN106433070A - Halogen-free flame-retardant PC (polycarbonate) material with electromagnetic shielding characteristics and method for preparing halogen-free flame-retardant PC material - Google Patents
Halogen-free flame-retardant PC (polycarbonate) material with electromagnetic shielding characteristics and method for preparing halogen-free flame-retardant PC material Download PDFInfo
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- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
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- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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Abstract
The invention relates to the field of electromagnetic shielding composite materials, in particular to a halogen-free flame-retardant PC (polycarbonate) material with electromagnetic shielding characteristics and a method for preparing the halogen-free flame-retardant PC material. The halogen-free flame-retardant PC material comprises, by weight, PC resin, polycarbonate-polyorganosiloxane copolymers, carbon fibers of stainless steel fiber bundles, carbon nano-tubes, dethylene butylaerylate copolymers, silica acrylic resin copolymers, poly-aryl phosphate ester, flame retardants, flame-retardant synergists, polytetrafluoroethylene, antioxidants 612S, antioxidants 1076 and pentaerythritol stearate. The method includes pretreating the stainless steel fiber bundles; blending the stainless steel fiber bundles and other materials with one another to obtain mixtures and granulating the mixtures to obtain the halogen-free flame-retardant PC material with the electromagnetic shielding characteristics. The halogen-free flame-retardant PC material and the method have the advantages of excellent conducting properties, shielding efficiency, flame-retardant characteristics, strength and toughness, convenience in processing and operation and high efficiency.
Description
Technical field
The present invention relates to electromagnetic shielding composite material field, more particularly to a kind of halogen-free flameproof with electromagnetic shielding characteristic
PC material and preparation method thereof.
Background technology
The advantages such as high intensity, high tenacity, high heat resisting temperature and good electrology characteristic that Merlon has so as to
The electronics industry epoch are widely used, and the fast development with electronics and communications industry, produced by electronic equipment
Some electromagnetic radiation increasingly cause the concern of society, and these electromagnetic waves cause threat to the health of human body, and these
Strict requirements have all been carried out in electronic application field industry to fire-retardant and environmental protection, thus exploitation is with electromagnetic shielding characteristic
Halogen-free flame retardant PC material sense is very big.
Existing electromagnetic shielding composite material is mainly using the filler for adding with conductive characteristic at present（Conductive black, gold
Category powder）Or fiber（Conductive carbon fibre, stainless steel fibre, metallic fiber）Etc. being modified.But conductive black, carbon fiber
All have that poorly conductive, addition be big, the low shortcoming of shield effectiveness, while conductive black also has the technology difficulty for being difficult to add to deposit
?；Nickel, copper, ferrum, argentum powder belong to me tallic conductive filler, and good conductivity belongs to one-dimension type conductive filler yet with which, in modeling
Basic in material be present in powder, and the two dimension connection between conductive filler and bridging action become very weak, and then influence whether the phase
Shield effectiveness.
Stainless steel fibre is due to preferable sexual valence when processing characteristics, being commercially mainstream applications, main at present
Melt blending is carried out by directly adding stainless steel fibre in double screw extruder with plastics, the method easily causes rustless steel fibre
Dimension becomes very broken under screw rod shearing effect, while the abrasion to extruder gun barrel, screw rod is larger, practical operation is got up comprehensive effect
Really unsatisfactory.
Open east to cause to exist《The preparation of SSF_ABS and GF_PA6 composite and performance study》In point out to first pass through cable cladding
Technique prepares stainless steel fibre filling ABS masterbatch, adds blending in ABS composite material to take out grain master batch afterwards, and this method has
The directly contact for avoiding stainless steel fibre and screw rod of effect, reduces the friction damage to screw machine gun barrel, but master batch exists
After melting shearing blending with ABS, the draw ratio of stainless steel fibre inevitably declines, and then affects conductive and shielding effect
Really.
Chinese patent CN101812239B discloses a kind of preparation method of particle-filled conductive thermoplastic polymer, and carbon is received
Mitron, stainless steel fibre are respectively adopted special preparation technology and are molded into master batch, afterwards directly by conductive agglomerate and conducting base
Injection mo(u)lding product after resin physical blending.Find in practical operation due to the proportion of conductive agglomerate larger, especially rustless steel
Conductive agglomerate prepared by fiber, larger difference of specific gravity between these master batches and conducting base resin so that it is difficult to be thoroughly mixed
Uniformly, and the region of hopper blanking is easy to occur conductive agglomerate and is layered with conducting base resin and the unstable phenomenon of blanking,
And then cause the conductive characteristic fluctuation of injection mo(u)lding product very big.
Content of the invention
In order to overcome shortcoming and defect present in prior art, it is an object of the invention to provide a kind of have electromagnetic screen
The halogen-free flame retardant PC material of characteristic is covered, its conductive characteristic, shield effectiveness, flame-retarding characteristic and strength and toughness are excellent.
It is an object of the invention to provide a kind of preparation method of the halogen-free flame retardant PC material with electromagnetic shielding characteristic, its
Have the characteristics that easy processing operation, efficiency high.
The purpose of the present invention is achieved through the following technical solutions：
A kind of halogen-free flame retardant PC material with electromagnetic shielding characteristic, the raw material components comprising following mass percent：
PC resin 45-60%
Merlon-poly organo alkyl copolymer 5-15%
Stainless fiber beam 5-10%
Carbon fiber 5-10%
CNT 5-10%
Ethylene butyl acrylate copolymer 3-6%
Silica acrylic acid copolymer 2-6%
Poly aryl phosphate ester 8-12%
Fire retardant 0.08-0.1%
Fire retarding synergist 0.5-1%
Politef 0.1-0.4%
Antioxidant 612S 0.2-0.4%
Antioxidant 1076 0.1-0.2%
Pentaerythritol stearate 0.2-0.4%,
The total amount of above-mentioned raw materials is 100%, and wherein, the PC resin is bisphenol A polycarbonate, in 300 DEG C/1.2kg condition
Under, melt index is 10-30g/10min.
Wherein, in the Merlon-poly organo alkyl copolymer Organosiloxane block copolymer content in 10-
20wt%, can be effectively improved the percussion of material.The Merlon-poly organo alkyl copolymer hereinafter referred to as PC-
PDMS.
Wherein, the fire retardant be perfluoro butyl sulfosalt, one or two the combination in sulfobenzide. sulfonate.
Wherein, the fire retarding synergist is the organosilicon auxiliary agent containing phenyl functional group, and the presence of phenyl can be greatly reinforced
Fire retardant and the affinity of PC molecule, improve the compatibility of fire retardant and makrolon material, and organosilicon primarily serves fire-retardant fire
The effect of flame diffusion.Preferably, fire retarding synergist is one or more of FCA-107, FCA-117 of DOW CORNING.
Wherein, the silica acrylic acid copolymer is the graft copolymer of organosilicon and acrylic resin.Acrylic resin is made
Strengthen its compatibility with Merlon for the shell of core-shell copolymerized thing, the flexibility that silicon strand has can be mentioned needed for material
Toughness.
A kind of preparation method of the halogen-free flame retardant PC material with electromagnetic shielding characteristic, comprises the following steps：
a）The pre-treatment of stainless fiber beam：Fiber-treating liquid is put in fiber treatment groove, then by stainless fiber beam
It is placed in solution tank, takes out after immersion treatment 25-35min, then deionized water is cleaned 3 times, then by stainless fiber beam
Dry in 90-110 DEG C, then stainless fiber beam is put into ethanol of the 3- aminopropyl triethoxysilane content for 0.5-1.5wt%
1-2h being soaked in solution, stirs a solution every 25-35min, finally stainless fiber beam is taken out and dry in 90-110 DEG C
Dry；
The present invention processes stainless fiber beam using fiber-treating liquid, eliminates the impurity on its surface, and directly using silane idol
Connection agent coating infiltration carries out surface modification, greatly improves the compatibility with plastics.
b）Extruding pelletization：By above-mentioned formula ratio by PC resin, Merlon-poly organo alkyl copolymer, ethylene propylene
Olefin(e) acid acrylate copolymer, silica acrylic acid copolymer, poly aryl phosphate ester, fire retardant, fire retarding synergist, politef, anti-
Added by main feeding after oxygen agent 612S, antioxidant 1076, pentaerythritol stearate mix homogeneously；CNT, carbon fiber by
Side feeding is added；Using infiltrated with molten metal method, distraction step a）Stainless fiber beam after process is by strengthening thermoplastic composite material
Material infiltration mould addition, pelletizing afterwards, prepare the halogen-free flame retardant PC material with electromagnetic shielding characteristic.
The present invention strengthens thermoplastic composite mould using the filling of existing roving glass fiber, directly utilization by plastics with stainless
Steel fiber bundle is blended together, and at utmost remains draw ratio and the conductive characteristic of stainless steel fibre, while reducing processing journey
Sequence.Carbon fiber, CNT is introduced, can suitably reduce the consumption of stainless fiber beam, drop while the cost for reducing material
Its proportion low, enhances the strength of materials；The present invention is compounding with Sulfonateses using halogen-free flame retardants aryl phosphate ester, and adds
Fire retarding synergist lifting improves material flame-retarding characteristic；Also improve material using Merlon-poly organo alkyl copolymer
Toughness and surface effect.
Wherein, step a）In stainless fiber beam filament diameter be 12-15 μm, preferably 13 μm.
Wherein, step a）In fiber-treating liquid mixed by following components：2000 parts of deionized water, permanganic acid
Potassium 60-120 part, 400-800 part concentrated sulphuric acid.
Wherein, the addition of the stainless fiber beam by the engine speed of extruder and the pressure roller rotating speed of traction machine come
Adjust, it is 60-100r/min that the engine speed is 300-480r/min, traction machine pressure roller rotating speed.To stainless fiber beam
Filling content can achieve on-line control control, improve the overall mechanical properties of material.
Wherein, step b）In, the specific process parameter of double screw extruder is：One area's temperature is 220-240 DEG C, two
Area's temperature is 235-250 DEG C, and three area's temperature are that 245-255 DEG C, four area's temperature are 250-260 DEG C, and five area's temperature are 260-265
DEG C, six area's temperature are that 260-265 DEG C, seven area's temperature are 260-265 DEG C, and it is 255- that eight area's temperature are 255-260 DEG C, nine area's temperature
260 DEG C, it is 300-480r/min that ten area's temperature are 255-260 DEG C, screw speed.
The beneficial effects of the present invention is：
1 present invention introduces carbon fiber, CNT, can reduce the consumption of stainless fiber beam, the cost of material of reduction material
While reduce the proportion of stainless steel fibre, enhance the intensity of halogen-free flame retardant PC material of the present invention；
2nd, the present invention is compounding by aryl phosphate ester and halogen-free flame retardants, and adds fire retarding synergist to improve material flame-retarding characteristic
3rd, the present invention improved using Merlon-poly organo alkyl copolymer the toughness of halogen-free flame retardant PC material of the present invention with
Surface effect；
4th, the present invention is by the rationally compounding of various raw materials, the conductive features of the material for obtaining are excellent, surface resistivity ＜
103, shield effectiveness is strong, reaches as high as 69dB, and flame-retarding characteristic reaches V0, intensity and good-toughness.
Another beneficial effect of the present invention：
1st, the present invention processes stainless fiber beam using fiber-treating liquid, eliminates the impurity on its surface, and directly using silane
Coupling agent coating infiltration carries out surface modification, greatly improves the compatibility with plastics；
2nd, by the improvement to processing step, on-line control control can achieve to the filling content of stainless fiber beam, improves
The overall mechanical properties of material.
3rd, the present invention strengthens thermoplastic composite mould using the filling of existing roving glass fiber, directly using by plastics and not
Rust steel fiber bundle be blended together, at utmost remain draw ratio and the conductive characteristic of stainless steel fibre, at the same reduce plus
Engineering sequence.
4th, the preparation method of the present invention is simply ripe, production efficiency height, is conducive to popularity application.
Specific embodiment
For the ease of the understanding of those skilled in the art, with reference to embodiment, the present invention is further illustrated, real
The content that the mode of applying is referred to not limitation of the invention.
Embodiment 1
A kind of halogen-free flame retardant PC material with electromagnetic shielding characteristic, the raw material components comprising following mass percent：
PC resin 45.42%
PC-PDMS 15.00%
Stainless fiber beam 5.00%
Carbon fiber 10.00%
CNT 10.00%
Ethylene butyl acrylate copolymer 3.00%
Silica acrylic acid copolymer 2.00%
Poly aryl phosphate ester 8.00%
Perfluoro butyl sulfosalt 0.08%
Organic silicon flame-retardant synergist 0.70%
Politef 0.30%
Antioxidant 612S 0.20%
Antioxidant 1076 0.10%
Pentaerythritol stearate 0.20%.
A kind of preparation method of halogen-free flame retardant PC material with electromagnetic shielding characteristic of the present embodiment, it includes following system
Standby step：
a）The pre-treatment of stainless fiber beam：Fiber-treating liquid is put in fiber treatment groove, then by continuous rustless steel fibre
Dimension bundle is placed in solution tank, immersion treatment 30min, is put into deionized water in tank afterwards and is cleaned 3 times, has cleaned taking-up juxtaposition
Dry in 90 DEG C of baking ovens.Stainless fiber beam is put into the silane coupler of 0.5wt% afterwards（3- aminopropyl-triethoxy silicon
Alkane）In ethanol solution, 1h being soaked, a solution is stirred every 30min, after process, fibre bundle is taken out and be placed in 90 DEG C of baking ovens
Dry.
Step a）In fiber-treating liquid mixed by following components：Deionized water 2000ml, potassium permanganate
60g, mass concentration is 98% concentrated sulphuric acid 400ml.
b）Extruding pelletization：By above-mentioned formula ratio by PC resin, Merlon-poly organo alkyl copolymer（PC-PDMS）,
Ethylene butyl acrylate copolymer, silica acrylic acid copolymer, poly aryl phosphate ester, perfluoro butyl sulfosalt, organic silicon flame-retardant
Synergist, politef, antioxidant 612S, antioxidant 1076, pentaerythritol stearate are through high-speed mixer mix homogeneously
Added by main feeding afterwards；CNT, carbon fiber is added by side feeding；Using infiltrated with molten metal method, draw stainless fiber beam and lead to
Enhancing thermoplastic composite infiltration mould is crossed, under the premise of standing screw rotating speed, adjusting pressure roller rotating speed makes stainless fiber beam
Content control 5%, after through double screw extruder extruding pelletization, the pelleter pelletizing of employing, prepare special with electromagnetic shielding
The halogen-free flame retardant PC material of property.
The specific process parameter of double screw extruder is：One area's temperature is 230 DEG C, and two area's temperature are 240 DEG C, three area's temperature
For 250 DEG C, four area's temperature are that 260 DEG C, five area's temperature are 265 DEG C, and six area's temperature are that 265 DEG C, seven area's temperature are 265 DEG C, 8th area
Temperature is 260 DEG C, and nine area's temperature are that 260 DEG C, ten area's temperature are 260 DEG C, and screw speed is that 450r/min, the pressure roller of traction machine turns
Speed is 72r/min.
Embodiment 2
A kind of halogen-free flame retardant PC material with electromagnetic shielding characteristic, the raw material components comprising following mass percent：
PC resin 49.42%
PC-PDMS 8.00%
Stainless fiber beam 6.50%
Carbon fiber 8.50%
CNT 8.50%
Ethylene butyl acrylate copolymer 4.50%
Silica acrylic acid copolymer 3.00%
Poly aryl phosphate ester 9.50%
Perfluoro butyl sulfosalt 0.08%
Organic silicon flame-retardant synergist 1.00%
Politef 0.20%
Antioxidant 612S 0.20%
Antioxidant 1076 0.20%
Pentaerythritol stearate 0.40%.
A kind of preparation method of halogen-free flame retardant PC material with electromagnetic shielding characteristic of the present embodiment, it includes following system
Standby step：
a）The pre-treatment of stainless fiber beam：Fiber-treating liquid is put in fiber treatment groove, then by continuous rustless steel fibre
Dimension bundle is placed in solution tank, immersion treatment 25min, is put into deionized water in tank afterwards and is cleaned 3 times, has cleaned taking-up juxtaposition
Dry in 100 DEG C of baking ovens.Stainless fiber beam is put into the silane coupler of 1wt% afterwards（3- aminopropyl-triethoxy silicon
Alkane）In ethanol solution, 2h being soaked, a solution is stirred every 25min, after process, stainless fiber beam is taken out and be placed in 100
Dry in DEG C baking oven.
Step a）In fiber-treating liquid mixed by following components：Deionized water 2000ml, potassium permanganate
120g, 800ml concentrated sulphuric acid.
b）Extruding pelletization：By formula ratio by PC resin, Merlon-poly organo alkyl copolymer（PC-PDMS）, ethylene
Butyl acrylate copolymer, silica acrylic acid copolymer, poly aryl phosphate ester, 0.08% perfluoro butyl sulfosalt, organosilicon hinders
Combustion synergist, politef, antioxidant 612S, 0.1% antioxidant 1076, pentaerythritol stearate are through high-speed mixer
Added by main feeding after mix homogeneously；CNT, carbon fiber is added by side feeding；Using infiltrated with molten metal method, rustless steel is drawn
Fibre bundle infiltrates mould by strengthening thermoplastic composite, and governing speed makes the content of stainless fiber beam control 6.5%,
After through double screw extruder extruding pelletization, the pelleter pelletizing of employing, prepare the halogen-free flameproof with electromagnetic shielding characteristic
PC material.
The specific process parameter of double screw extruder is：One area's temperature is 220 DEG C, and two area's temperature are 235 DEG C, three area's temperature
For 245 DEG C, four area's temperature are that 255 DEG C, five area's temperature are 260 DEG C, and six area's temperature are that 260 DEG C, seven area's temperature are 260 DEG C, 8th area
Temperature is 255 DEG C, and nine area's temperature are that 255 DEG C, ten area's temperature are 255 DEG C, and screw speed is that 420r/min, the pressure roller of traction machine turns
Speed is 80r/min.
Embodiment 3
A kind of halogen-free flame retardant PC material with electromagnetic shielding characteristic, the raw material components comprising following mass percent：
PC resin 52.20%
PC-PDMS 10.00%
Stainless fiber beam 7.00%
Carbon fiber 7.00%
CNT 5.00%
Ethylene butyl acrylate copolymer 4.00%
Silica acrylic acid copolymer 3.00%
Poly aryl phosphate ester 10.00%
Perfluoro butyl sulfosalt 0.10%
Organic silicon flame-retardant synergist 0.60%
Politef 0.30%
Antioxidant 612S 0.40%
Antioxidant 1076 0.10%
Pentaerythritol stearate 0.30%
A kind of preparation method of halogen-free flame retardant PC material with electromagnetic shielding characteristic of the present embodiment, it includes that following preparation walks
Suddenly：
a）The pre-treatment of stainless fiber beam：Fiber-treating liquid is put in fiber treatment groove, then by continuous rustless steel fibre
Dimension bundle is placed in solution tank, immersion treatment 30min, is put into deionized water in tank afterwards and is cleaned 3 times, has cleaned taking-up juxtaposition
Dry in 105 DEG C of baking ovens.Stainless fiber beam is put into the silane coupler of 1.5wt% afterwards（3- aminopropyl-triethoxy silicon
Alkane）In ethanol solution, 1.5h being soaked, a solution is stirred every 25min, after process, stainless fiber beam is taken out and be placed in
Dry in 100 DEG C of baking ovens.
Step a）In fiber-treating liquid mixed by following components：Deionized water 2000ml, potassium permanganate
100g, 600ml concentrated sulphuric acid.
b）Extruding pelletization：By formula ratio by PC resin, Merlon-poly organo alkyl copolymer（PC-PDMS）, ethylene
Butyl acrylate copolymer, silica acrylic acid copolymer, poly aryl phosphate ester, perfluoro butyl sulfosalt, organic silicon flame-retardant synergistic
Agent, politef, antioxidant 612S, antioxidant 1076, pentaerythritol stearate after high-speed mixer mix homogeneously by
Main feeding is added；CNT, carbon fiber is added by side feeding；Using infiltrated with molten metal method, stainless fiber beam is drawn by increasing
Heat-flash plastic composites infiltrate mould, and governing speed makes the content of stainless fiber beam control 7%, after squeeze through twin screw
Go out machine extruding pelletization, the pelleter pelletizing of employing, prepare the halogen-free flame retardant PC material with electromagnetic shielding characteristic.
The specific process parameter of double screw extruder is：One area's temperature is 240 DEG C, and two area's temperature are 250 DEG C, three area's temperature
For 255 DEG C, four area's temperature are that 250 DEG C, five area's temperature are 265 DEG C, and six area's temperature are that 265 DEG C, seven area's temperature are 265 DEG C, 8th area
Temperature is 260 DEG C, and nine area's temperature are that 260 DEG C, ten area's temperature are 255 DEG C, and screw speed is that 400r/min, the pressure roller of traction machine turns
Speed is 86r/min.
Embodiment 4
A kind of halogen-free flame retardant PC material with electromagnetic shielding characteristic, the raw material components comprising following mass percent：
PC resin 54.50%
PC-PDMS 7.50%
Stainless fiber beam 8.50%
Carbon fiber 8.50%
CNT 5.00%
Ethylene butyl acrylate copolymer 2.50%
Silica acrylic acid copolymer 4.00%
Poly aryl phosphate ester 8.00%
Perfluoro butyl sulfosalt 0.10%
Organic silicon flame-retardant synergist 0.60%
Politef 0.20%
Antioxidant 612S 0.20%
Antioxidant 1076 0.20%
Pentaerythritol stearate 0.20%.
A kind of preparation method of halogen-free flame retardant PC material with electromagnetic shielding characteristic of the present embodiment, it includes following system
Standby step：
a）The pre-treatment of stainless fiber beam：Fiber-treating liquid is put in fiber treatment groove, then by continuous rustless steel fibre
Dimension bundle is placed in solution tank, immersion treatment 25min, is put into deionized water in tank afterwards and is cleaned 3 times, has cleaned taking-up juxtaposition
Dry in 95 DEG C of baking ovens.Stainless fiber beam is put into the silane coupler of 1.5wt% afterwards（3- aminopropyl-triethoxy silicon
Alkane）In ethanol solution, 1h being soaked, a solution is stirred every 25min, after process, fibre bundle is taken out and be placed in 110 DEG C of baking ovens
Middle drying.
Step a）In fiber-treating liquid mixed by following components：Deionized water 2000ml, potassium permanganate
80g, 700ml concentrated sulphuric acid.
b）Extruding pelletization：By formula ratio by PC resin, Merlon-poly organo alkyl copolymer（PC-PDMS）, ethylene
Butyl acrylate copolymer, silica acrylic acid copolymer, poly aryl phosphate ester, perfluoro butyl sulfosalt, organic silicon flame-retardant synergistic
Agent, politef, antioxidant 612S, antioxidant 1076, pentaerythritol stearate after high-speed mixer mix homogeneously by
Main feeding is added；CNT, carbon fiber is added by side feeding；Using infiltrated with molten metal method, stainless fiber beam is drawn by increasing
Heat-flash plastic composites infiltrate mould, and governing speed makes the content of stainless fiber beam control 8.5%, after through twin screw
Extruder extruding pelletization, the pelleter pelletizing of employing, prepare the halogen-free flame retardant PC material with electromagnetic shielding characteristic.
The specific process parameter of double screw extruder is：One area's temperature is 220 DEG C, and two area's temperature are 235 DEG C, three area's temperature
For 245 DEG C, four area's temperature are that 255 DEG C, five area's temperature are 260 DEG C, and six area's temperature are that 260 DEG C, seven area's temperature are 260 DEG C, 8th area
Temperature is 255 DEG C, and nine area's temperature are that 255 DEG C, ten area's temperature are 255 DEG C, and screw speed is that 360r/min, the pressure roller of traction machine turns
Speed is 86r/min.
Embodiment 5
A kind of halogen-free flame retardant PC material with electromagnetic shielding characteristic, the raw material components comprising following mass percent：
PC resin 57.50%
PC-PDMS 5.00%
Stainless fiber beam 9.00%
Carbon fiber 5.00%
CNT 5.00%
Ethylene butyl acrylate copolymer 2.00%
Silica acrylic acid copolymer 3.00%
Poly aryl phosphate ester 12.00%
Perfluoro butyl sulfosalt 0.10%
Organic silicon flame-retardant synergist 0.70%
Politef 0.20%
Antioxidant 612S 0.20%
Antioxidant 1076 0.10%
Pentaerythritol stearate 0.20%.
A kind of preparation method of halogen-free flame retardant PC material with electromagnetic shielding characteristic of the present embodiment, it includes following system
Standby step：
a）The pre-treatment of stainless fiber beam：Fiber-treating liquid is put in fiber treatment groove, then by continuous rustless steel fibre
Dimension bundle is placed in solution tank, immersion treatment 25min, is put into deionized water in tank afterwards and is cleaned 3 times, has cleaned taking-up juxtaposition
Dry in 100 DEG C of baking ovens.Stainless fiber beam is put into the silane coupler of 1wt% afterwards（3- aminopropyl-triethoxy silicon
Alkane）In ethanol solution, 2h being soaked, a solution is stirred every 25min, after process, fibre bundle is taken out and be placed in 100 DEG C of baking ovens
Middle drying.
Step a）In fiber-treating liquid mixed by following components：Deionized water 2000ml, potassium permanganate
110g, 500ml concentrated sulphuric acid.
b）Extruding pelletization：By formula ratio by PC resin, Merlon-poly organo alkyl copolymer（PC-PDMS）, ethylene
Butyl acrylate copolymer, silica acrylic acid copolymer, poly aryl phosphate ester, 0.08% perfluoro butyl sulfosalt, organosilicon hinders
Combustion synergist, politef, antioxidant 612S, 0.1% antioxidant 1076, pentaerythritol stearate are through high-speed mixer
Added by main feeding after mix homogeneously；CNT, carbon fiber is added by side feeding；Using infiltrated with molten metal method, rustless steel is drawn
Fibre bundle infiltrates mould by strengthening thermoplastic composite, and governing speed makes the content of stainless fiber beam control 9%, it
By double screw extruder extruding pelletization, the pelleter pelletizing of employing, the halogen-free flame retardant PC with electromagnetic shielding characteristic is prepared
Material.
The specific process parameter of double screw extruder is：One area's temperature is 220 DEG C, and two area's temperature are 235 DEG C, three area's temperature
For 245 DEG C, four area's temperature are that 255 DEG C, five area's temperature are 260 DEG C, and six area's temperature are that 260 DEG C, seven area's temperature are 260 DEG C, 8th area
Temperature is 255 DEG C, and nine area's temperature are that 255 DEG C, ten area's temperature are 255 DEG C, and screw speed is that 340r/min, the pressure roller of traction machine turns
Speed is 95r/min.
The performance detection data of the electromagnetic shielding PC material of halogen-free flameproof obtained in 1 ~ embodiment of embodiments of the invention 5 is shown in
Table 1.
The performance detection data of the electromagnetic shielding PC material of halogen-free flameproof obtained in 1 ~ embodiment of embodiments of the invention 5 is shown in Table 1.
It can be seen from the above results that the mechanical property of the electromagnetic shielding PC material of the present invention is good, its conductive characteristic, screen
Cover efficiency, flame-retarding characteristic and strength and toughness excellent.
It can be seen from the above results that the mechanical property of the electromagnetic shielding PC material of the present invention is good, its conductive characteristic, screen
Cover efficiency, flame-retarding characteristic and strength and toughness excellent.
Above-described embodiment is the present invention preferably implementation, and in addition, the present invention can be realized with alternate manner, do not taken off
Any on the premise of the present inventive concept obvious replace all within protection scope of the present invention.
Claims (10)
1. a kind of halogen-free flame retardant PC material with electromagnetic shielding characteristic, it is characterised in that：Original comprising following mass percent
Material component：
PC resin 45-60%
Merlon-poly organo alkyl copolymer 5-15%
Stainless fiber beam 5-10%
Carbon fiber 5-10%
CNT 5-10%
Ethylene butyl acrylate copolymer 3-6%
Silica acrylic acid copolymer 2-6%
Poly aryl phosphate ester 8-12%
Fire retardant 0.08-0.1%
Fire retarding synergist 0.5-1%
Politef 0.1-0.4%
Antioxidant 612S 0.2-0.4%
Antioxidant 1076 0.1-0.2%
Pentaerythritol stearate 0.2-0.4%,
The total amount of above-mentioned raw materials is 100%, and wherein, the PC resin is that melt index is under 300 DEG C/1.2kg test condition
The bisphenol A polycarbonate of 10-30g/10min.
2. a kind of halogen-free flame retardant PC material with electromagnetic shielding characteristic according to claim 1, it is characterised in that：Described
In Merlon-poly organo alkyl copolymer, the content of polysiloxane block is in 10-20wt%.
3. a kind of halogen-free flame retardant PC material with electromagnetic shielding characteristic according to claim 1, it is characterised in that：Described
Fire retardant is perfluoro butyl sulfosalt, one or two the combination in sulfobenzide. sulfonate.
4. a kind of halogen-free flame retardant PC material with electromagnetic shielding characteristic according to claim 1, it is characterised in that：Described
Fire retarding synergist is the organosilicon auxiliary agent containing phenyl functional group.
5. a kind of halogen-free flame retardant PC material with electromagnetic shielding characteristic according to claim 1, it is characterised in that：Described
Silica acrylic acid copolymer is the graft copolymer of organosilicon and acrylic resin.
6. a kind of preparation method of the halogen-free flame retardant PC material with electromagnetic shielding characteristic described in any one of claim 1-5, its
It is characterised by：Comprise the following steps：
a）The pre-treatment of stainless fiber beam：Fiber-treating liquid is put in fiber treatment groove, then by stainless fiber beam
It is placed in solution tank, takes out after immersion treatment 25-35min, then deionized water is cleaned 2-3 time, then by stainless steel fibre
Restraint and dry in 90-110 DEG C；Again stainless fiber beam is put into second of the 3- aminopropyl triethoxysilane content for 0.5-1.5wt%
Alcohol solution for soaking 1-2h, stirs a solution every 25-35min, finally takes out and stainless fiber beam in 90-110 DEG C
Dry；
b）Extruding pelletization：Will be common to PC resin, Merlon-poly organo alkyl copolymer, ethylene butyl acrylate by formula ratio
Polymers, silica acrylic acid copolymer, poly aryl phosphate ester, fire retardant, fire retarding synergist, politef, antioxidant 612S, anti-
Added by main feeding after oxygen agent 1076 and pentaerythritol stearate mix homogeneously；CNT and carbon fiber are added by side feeding
Enter；Using infiltrated with molten metal method, distraction step a）Stainless fiber beam after process is prepared by infiltration mould, afterwards pelletizing
Halogen-free flame retardant PC material with electromagnetic shielding characteristic.
7. the preparation method of a kind of halogen-free flame retardant PC material with electromagnetic shielding characteristic according to claim 6, which is special
Levy and be：Step a）In stainless fiber beam filament diameter be 10-15 μm.
8. the preparation method of a kind of halogen-free flame retardant PC material with electromagnetic shielding characteristic according to claim 6, which is special
Levy and be：Step a）In fiber-treating liquid mixed by following components：Potassium permanganate 60-120 part, concentrated sulphuric acid 400-
800 parts and 2000 parts of deionized water.
9. the preparation method of a kind of halogen-free flame retardant PC material with electromagnetic shielding characteristic according to claim 6, which is special
Levy and be：The addition of the stainless fiber beam is adjusted by the engine speed of extruder and the pressure roller rotating speed of traction machine,
Engine speed is 300-480r/min, and traction machine pressure roller rotating speed is 60-100r/min.
10. the preparation method of a kind of halogen-free flame retardant PC material with electromagnetic shielding characteristic according to claim 6, which is special
Levy and be：Step b）In, the specific process parameter of double screw extruder is：One area's temperature is 220-240 DEG C, two area's temperature
For 235-250 DEG C, three area's temperature are that 245-255 DEG C, four area's temperature are 250-260 DEG C, and five area's temperature are 260-265 DEG C, 6th area
Temperature is 260-265 DEG C, and seven area's temperature are that 260-265 DEG C, eight area's temperature are 255-260 DEG C, and nine area's temperature are 255-260 DEG C,
Ten area's temperature are 255-260 DEG C, and screw speed is 300-480r/min.
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| CN108276755A (en) * | 2018-03-02 | 2018-07-13 | 合肥思博特软件开发有限公司 | A kind of composite material and preparation method for electromagnetic shielding |
| CN108504063A (en) * | 2017-02-28 | 2018-09-07 | 汉达精密电子(昆山)有限公司 | Halogen-free flame retardant PC/CF composite materials and products thereof |
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| CN112194886A (en) * | 2020-09-10 | 2021-01-08 | 金旸（厦门）新材料科技有限公司 | Extrusion-grade polycarbonate alloy material for interior trim panel of passenger car and preparation method thereof |
| CN112538193A (en) * | 2020-12-16 | 2021-03-23 | 上海中镭新材料科技有限公司 | Dual-mode carbon fiber, preparation method thereof and application thereof in PC/ABS alloy material |
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Effective date of registration: 20190426 Address after: 523000 Nan Ge industrial area, Dao Jiao Town, Dongguan, Guangdong Patentee after: DONGGUAN SILVER AGE OPTOELECTRONICS SCI. & TECH. CO., LTD. Address before: 523187 Nange Industrial Zone, Daojiao Town, Dongguan City, Guangdong Province Patentee before: Silver Age Engineering Plastic (Dongguan) Co., Ltd. |