CN107177184A - A kind of anlistatig fire retardation PC/ABS compositions - Google Patents
A kind of anlistatig fire retardation PC/ABS compositions Download PDFInfo
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- CN107177184A CN107177184A CN201710492706.8A CN201710492706A CN107177184A CN 107177184 A CN107177184 A CN 107177184A CN 201710492706 A CN201710492706 A CN 201710492706A CN 107177184 A CN107177184 A CN 107177184A
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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
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/44—Polyester-amides
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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/017—Additives being an antistatic agent
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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
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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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
- C08L2201/00—Properties
- C08L2201/04—Antistatic
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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
- 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
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a kind of anlistatig fire retardation PC/ABS compositions, including：50 70 parts by weight PC, 10 20 parts by weight ABS, the triblock copolymer of 3 15 parts by weight poly- (styrene)/poly- (butadiene)/poly- (methyl methacrylate), 10 20 parts by weight polyether ester amides, 0.5 2 parts by weight of inorganic antistatic additive, 6 20 parts by weight composite flame-retardant agents, 0.1 1 parts by weight antioxidant, and 0.5 2 parts by weight lubricants；The product prepared using said composition is while with good mechanical properties, with excellent antistatic property and anti-flammability etc..The present invention also discloses the preparation method of above-mentioned composition.
Description
Technical field
The invention belongs to technical field of polymer materials, and in particular to a kind of anlistatig fire retardation PC/ABS compositions and its
Preparation method.
Background technology
PC is a kind of armorphous thermoplastic engineering plastic of high comprehensive performance, tasteless, odorless, transparent, with good
Mechanical property, especially excellent shock resistance, good stability of the dimension.But it is low there is also endurance life, easily producing should
Power ftractures, and notch sensitive wears no resistance.Meanwhile, PC is in polarity, and the presence of ester group causes its electrical insulating property than nonpolar polymerization
Thing is poor.Acrylonitrile-butadiene-styrene (ABS) (ABS) resin has higher impact strength, heat resistance and dimensional stability, comprehensive
Function admirable, it is easy to process, due to the various advantages that it has, is widely used in industrial spare and accessory parts, electric equipment products
Shell and driving member, office equipment, and other fields.
ABS resin and PC resin are blended, ABS heat resistance and mechanical property is on the one hand improved, on the other hand drops
Low PC costs and melt viscosity, improve mobility, can improve its processability, reduce product internal stress and impact strength to system
The sensitiveness of product thickness, obtained blend alloy performance is between ABS and PC, both with higher impact strength, flexure
Property, rigidity and heat resistance, while having good processing characteristics again, and improve chemical-resistant and low-temperature flexibility, thermal deformation
10 DEG C high than ABS or so of temperature.
PC/ABS alloys are widely used in the field such as automobile, machinery, electric, office equipment, the instrument of such as automobile
Disk, door-plate, wheel cover, pressure fan, notebook computer, the shell of Printers and Faxes machine, shock proof helmet cap etc..
Still suffered from reality and PC/ABS composition articles are further improved in terms of antistatic property, fire resistance
Demand.
The content of the invention
It is an object of the invention to a kind of anlistatig fire retardation PC/ABS compositions and preparation method thereof, said composition is utilized
The product of preparation is while with good mechanical properties, with excellent antistatic property and anti-flammability.
Technical scheme is as follows：
A kind of anlistatig fire retardation PC/ABS compositions, including：50-70 parts by weight PC, 10-20 parts by weight ABS, 3-15 weight
Measure the triblock copolymer of part poly- (styrene)/poly- (butadiene)/poly- (methyl methacrylate), 10-20 parts by weight polyether esters
Acid amides, 0.5-2 parts by weight of inorganic antistatic additive, 6-20 parts by weight composite flame-retardant agents, 0.1-1 parts by weight antioxidant, and 0.5-2 weights
Measure part lubricant.
PC can be using Products such as husky primary radical innovations plastics, Japanese Supreme Being people's chemical conversions, and viscosity average molecular weigh is 18000-
25000。
ABS is using Products such as Japanese Daicel, eastern beautiful, Asahi Chemical Industries.
The triblock copolymer of poly- (styrene)/poly- (butadiene)/poly- (methyl methacrylate), using Arkema
Obtained trade name Nanostrength 123,250,012, E20, E40 product.
Polyether ester amides are made by the following method, and 12- amido lauric acid/dodecanoic acids, terephthaldehyde are inserted in autoclave
After replacing in autoclave with nitrogen, (0.3~0.5MPa) is pressurizeed in 220-230 DEG C by acid, antioxidant 1010, Yi Jishui
Closed lower heating stirring 4-5 hours, obtaining two ends had the polyamide of carboxyl.
Secondly polyethylene glycol and zirconium acetate that number-average molecular weight is 500-1000 are added, in 230-250 DEG C, 0.12kPa
It polymerize 4-6 hours under following decompression to obtain sticky polymer.This polymer is carried out with being taken out on tape in thread
Granulation obtains polyether ester amides.
Inorganic antistatic agent uses lithium chloride, potassium chloride, calcium chloride, magnesium chloride, lithium bromide, sodium bromide, KBr, bromination
One or more in calcium, magnesium bromide.
Composite flame-retardant agent uses phosphate compounds with polytetrafluoroethylene (PTFE) using part by weight as 3-20:1 combination, phosphoric acid
Ester type compound is selected from triphenyl phosphate, three (2,6- xylyl) phosphates, with double (two (2, the 6- xylyls) of resorcinol
Phosphate) as the phosphoric acid ester oligomer of main body, 4,4- dihydroxydiphenyls double (diphenyl phosphates) as main body phosphate
Oligomer, the phosphoric acid ester oligomer for being used as using bisphenol-A double (diphenyl phosphate) main body；
Antioxidant is antioxidant 1010 and 168 with 1:Mixture of 1 weight than formation.
Lubricant is one kind or its mixture in pentaerythritol tetrastearate, calcium stearate, ethylene bis stearamide.
The preparation method of above-mentioned anlistatig fire retardation PC/ABS compositions, including step are provided simultaneously：
a：The three of PC, ABS and poly- (styrene)/poly- (butadiene)/poly- (methyl methacrylate) are weighed by weight ratio
Block copolymer, is well mixed；
b：Polyether ester amides, inorganic antistatic agent, composite flame-retardant agent, antioxidant and lubricant are weighed by weight ratio, are mixed
Close uniform, then it is added to continuation in high-speed mixer together with the material that a steps are mixed and mix until uniform；
c：The raw material that b step is mixed puts into the loading hopper of double screw extruder, through melting extrusion, granulates, fully
Plasticizing, melting, it is compound, extruded, tie rod, cooling, pelletizing, drying and pack again；
Technological parameter is as follows：210-230 DEG C of one area of double screw extruder, 210-230 DEG C of 2nd area, 210-230 DEG C of 3rd area, four
210-230 DEG C of area, 220-240 DEG C of 5th area, 220-240 DEG C of 6th area, 215-230 DEG C of 7th area, 210-230 DEG C of 8th area；Screw rod revolution
Control is in 300-400rpm；2~10min of residence time.
In the present invention, the polyether ester amides with specific structure prepared by using above-mentioned ad hoc approach are added to combination
Thing, and it is equipped with inorganic antistatic agent so that product is while with good mechanical properties, also with excellent antistatic behaviour
Can, the operation soaked even across such as water, its surface resistivity also changes very little；Product has good compatibility simultaneously.
, can be in the case of using less consumption so that composition has good by using above-mentioned composite flame-retardant agent
Fire resistance, reach UL94V-0 ranks.
The product prepared using the present composition, can be widely used for automobile, household electrical appliances, communication apparatus, electric part
Deng field, sheathing material, container material etc. are used for example as.
Embodiment
Technical scheme is further detailed and described below by way of embodiment.
Polyether ester amides Production Example
Adopt and prepare with the following method：
The parts by weight of 12- amidos lauric acid/dodecanoic acid 106.4, the weight of terephthalic acid (TPA) 3.6 are inserted in the autoclave of stainless steel
Part, 0.3 parts by weight antioxidant 1010 and the parts by weight of water 7 are measured, after replacing in autoclave with nitrogen, in 220 DEG C of pressurizations
(0.5MPa) closed lower heating stirring 4 hours, obtaining two ends of acid number 22.8 has the parts by weight of polyamide 106 of carboxyl.
Secondly add Mn500 the parts by weight of polyethylene glycol 180 and the parts by weight of zirconium acetate 0.8, in 240 DEG C, 0.12kPa with
Under decompression under polymerization 5 hours to obtain sticky polymer.This polymer is granulated with being taken out on tape in thread
Obtain polyether ester amides.
Embodiment
Anlistatig fire retardation PC/ABS composition particles are prepared by the following method：
a：The three of PC, ABS and poly- (styrene)/poly- (butadiene)/poly- (methyl methacrylate) are weighed by weight ratio
Block copolymer, is well mixed；
b：Polyether ester amides (or organic antistatic agentses a or b), inorganic antistatic agent, composite flame-proof are weighed by weight ratio
Agent (or triphenyl phosphate, or brominated styrene and PTFE (teflon 6J) mixture), antioxidant and lubricant, mixing is equal
It is even, then it is added to together with the material that a steps are mixed in high-speed mixer and continues to mix until uniform；
c：The raw material that b step is mixed puts into the loading hopper of double screw extruder, through melting extrusion, granulates, fully
Plasticizing, melting, it is compound, extruded, tie rod, cooling, pelletizing, drying and pack again；
Technological parameter is as follows：210 DEG C of one area of double screw extruder, 210 DEG C of 2nd area, 215 DEG C of 3rd area, 220 DEG C of 4th area, 5th area
230 DEG C, 225 DEG C of 6th area, 220 DEG C of 7th area, 210 DEG C of 8th area；Screw rod revolution is controlled in 350rpm；Residence time 6min.
PC is melted into the L-1225WP products of company using Supreme Being people, and number-average molecular weight is 22400；ABS resin：Using Daicel
The products C evian-V 320 of company；The triblock copolymer of poly- (styrene)/poly- (butadiene)/poly- (methyl methacrylate)
Thing, using the product of trade name Nanostrength 123 made from Arkema；Polyether ester amides use above-mentioned polyethers
Product made from esteramides Production Example；Organic antistatic agentses a：Using Pelestat NC6321, Japanese Sanyo companies, polyether ester
Amide-type polymer；Organic antistatic agentses b：Using Pebax MV-1074, Arkema companies, polyetheramides type polymer；It is inorganic
Antistatic additive uses lithium bromide, from commercially available；In composite flame-retardant agent, phosphate uses the CR-741 of big eight chemical industrial company,
It is the phosphate with bisphenol-A double (diphenyl phosphates) for main component；Polytetrafluoroethylene (PTFE) is using three fluorine chemistry companies of well Du Pont
Teflon (registration mark) 6J；Both part by weight are 9：1；Triphenyl phosphate, from commercially available；Brominated styrene and three wells are shut out
The teflon 6J of fluorine chemistry company of nation presses 9:1 weight is than the mixture of formation, and wherein brominated styrene is from commercially available；Antioxidant
It is antioxidant 1010 and 168 with 1:Mixture of 1 weight than formation；Lubricant is pentaerythritol tetrastearate, from commercially available.
Embodiment 1-5 and comparative example 1-6 each components weight consumption and properties of product are shown in Table 1.Performance test：
Tensile property test is carried out by ISO 527-2, and specimen size is 150*10*4, and draw speed is 50mm/min；It is curved
Bent performance test is carried out by ISO 178, and specimen size is 80*10*4, and draw speed is 2mm/min, and span is 64mm；Impact is strong
Degree：To injection-molded article, it is measured with ASTM D256 (there is indentation, 3.2mm is thick) method A.Heat resistance is according to ASTM D-
648 determine load deflection temperature (experiment chip size under 1.82MPa loads：127mm*12.7mm*6.4mm)
Antistatic behaviour [according to ASTM D257]
(1) surface resistivity：Using injection-molded article as test piece, by the test piece in 23 DEG C, humidity 50%RH bar
After standing 48 hours under part, entered with teraohmmeter [ADVANTEST limited companies system, below equally] under identical environment
Row is determined.
(2) surface resistivity after washing：Prepare with (1) identical test piece, using 23 DEG C of ion exchange water 100ml with
100ml/ points of flow is washed after tilted-putted test film, is dried 3 hours with 80 DEG C of temperature in air circulation drying box.
After the step 15 time that washing-drying is repeated, the test piece is stood 48 hours under conditions of 23 DEG C, humidity 50%RH,
Then it is measured with teraohmmeter under identical environment.
(3) specific insulation：Identical test film is tested using with surface resistivity, is measured in the same way
[according to ASTM D257].Anti-flammability：According to UL 94V standard testings, sample thickness 0.8mm.
Table 1
From the test result shown in table 1, the product prepared using the composition of the application specific structure and composition,
While with mechanical performances such as good stretching, shock resistances, with excellent antistatic property and anti-flammability, and in warp
Go through after water washing operations, still with good antistatic property.
And during without using or using other kinds of polyethers (ester) amide-type antistatic additive, under its antistatic property is obvious
Drop, while when inorganic antistatic agent and above-mentioned polyethers (ester) amide-type organic antistatic agentses not being applied in combination, composition article
Antistatic property also reduce, especially wash after surface resistivity significantly increase；During using other kinds of fire retardant,
The fire resistance of composition article is significantly lower than the fire resistance of the composite flame-retardant agent using the application.
The foregoing is only a preferred embodiment of the present invention, therefore can not limit the scope that the present invention is implemented according to this, i.e.,
The equivalent changes and modifications made according to the scope of the claims of the present invention and description, all should still belong in the range of the present invention covers.
Claims (7)
1. a kind of anlistatig fire retardation PC/ABS compositions, it is characterised in that including following component：50-70 parts by weight PC, 10-
The triblock copolymer of 20 parts by weight ABS, 3-15 parts by weight poly- (styrene)/poly- (butadiene)/poly- (methyl methacrylates),
10-20 parts by weight polyether ester amides, 0.5-2 parts by weight of inorganic antistatic additive, 6-20 parts by weight composite flame-retardant agents, 0.1-1 weight
Part antioxidant, and 0.5-2 parts by weight lubricants, wherein, polyether ester amides are made by the following method, are put in autoclave
Enter 12- amido lauric acid/dodecanoic acids, terephthalic acid (TPA), antioxidant 1010, Yi Jishui, after being replaced in autoclave with nitrogen, in
220-230 DEG C of pressurization (0.3~0.5MPa) closed lower heating stirring 4-5 hours, obtaining two ends has the polyamide of carboxyl；Its
It is secondary to add the polyethylene glycol and zirconium acetate that number-average molecular weight is 500-1000, in 230-250 DEG C, below 0.12kPa decompression
Lower polymerization 4-6 hours is to obtain sticky polymer；This polymer granulate being gathered to take out in thread on tape
Polyetheresteramide；Composite flame-retardant agent uses phosphate compounds with polytetrafluoroethylene (PTFE) using part by weight as 3-20:1 combination.
2. composition as claimed in claim 1, it is characterised in that the viscosity average molecular weigh of PC resin is 18000-25000.
3. composition as claimed in claim 1, it is characterised in that inorganic antistatic agent uses lithium chloride, potassium chloride, chlorination
One or more in calcium, magnesium chloride, lithium bromide, sodium bromide, KBr, calcium bromide, magnesium bromide, preferably lithium chloride, bromination
Lithium.
4. composition as claimed in claim 1, it is characterised in that antioxidant is antioxidant 1010 and 168 with 1:1 weight compares shape
Into mixture.
5. composition as claimed in claim 1, it is characterised in that lubricant be pentaerythritol tetrastearate, calcium stearate,
One kind or its mixture in ethylene bis stearamide, preferably pentaerythritol tetrastearate.
6. composition as claimed in claim 1, it is characterised in that phosphate compounds are selected from triphenyl phosphate, three (2,6-
Xylyl) phosphate, with resorcinol double (two (2,6- xylyl) phosphates) as main body phosphoric acid ester oligomer, 4,
4- dihydroxydiphenyls double (diphenyl phosphates) as main body phosphoric acid ester oligomer, using bisphenol-A double (diphenyl phosphates) as
The phosphoric acid ester oligomer of main body.
7. the preparation method of anlistatig fire retardation PC/ABS compositions as claimed in claim 1, comprises the following steps：
a：The three block of PC, ABS and poly- (styrene)/poly- (butadiene)/poly- (methyl methacrylate) is weighed by weight ratio
Copolymer, is well mixed；
b：Polyether ester amides, inorganic antistatic agent, composite flame-retardant agent, antioxidant and lubricant are weighed by weight ratio, and mixing is equal
It is even, then it is added to together with the material that a steps are mixed in high-speed mixer and continues to mix until uniform；
c：The raw material that b step is mixed puts into the loading hopper of double screw extruder, through melting extrusion, granulates, fully plastify,
Melting, it is compound, extruded, tie rod, cooling, pelletizing, drying and pack again；
Technological parameter is as follows：210-230 DEG C of one area of double screw extruder, 210-230 DEG C of 2nd area, 210-230 DEG C of 3rd area, 4th area
210-230 DEG C, 220-240 DEG C of 5th area, 220-240 DEG C of 6th area, 215-230 DEG C of 7th area, 210-230 DEG C of 8th area；Screw rod revolution control
System is in 300-400rpm；2~10min of residence time.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110561871A (en) * | 2019-09-20 | 2019-12-13 | 厦门长塑实业有限公司 | Transparent flame-retardant antistatic polyamide film and preparation method thereof |
| CN111205587A (en) * | 2019-08-02 | 2020-05-29 | 杭州金州高分子科技有限公司 | Antistatic high-strength ABS (acrylonitrile-butadiene-styrene) modified material and preparation method thereof |
| CN114230999A (en) * | 2021-11-23 | 2022-03-25 | 金旸（厦门）新材料科技有限公司 | Halogen-free flame-retardant antistatic polycarbonate resin composition and preparation method thereof |
| CN115926452A (en) * | 2022-12-21 | 2023-04-07 | 上海金发科技发展有限公司 | Thin-wall high-light-transmittance flame-retardant nylon composite material and preparation method and application thereof |
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| CN106349678A (en) * | 2016-10-14 | 2017-01-25 | 上海金发科技发展有限公司 | Antistatic anti-flaming PC/ABS compound material and preparation method thereof |
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| CN111205587A (en) * | 2019-08-02 | 2020-05-29 | 杭州金州高分子科技有限公司 | Antistatic high-strength ABS (acrylonitrile-butadiene-styrene) modified material and preparation method thereof |
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| CN114230999A (en) * | 2021-11-23 | 2022-03-25 | 金旸（厦门）新材料科技有限公司 | Halogen-free flame-retardant antistatic polycarbonate resin composition and preparation method thereof |
| CN115926452A (en) * | 2022-12-21 | 2023-04-07 | 上海金发科技发展有限公司 | Thin-wall high-light-transmittance flame-retardant nylon composite material and preparation method and application thereof |
| CN115926452B (en) * | 2022-12-21 | 2024-05-14 | 上海金发科技发展有限公司 | Thin-wall high-light-transmittance flame-retardant nylon composite material and preparation method and application thereof |
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