CN107090168A - A kind of anlistatig PC/ABS compositions - Google Patents
A kind of anlistatig PC/ABS compositions Download PDFInfo
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- CN107090168A CN107090168A CN201710492746.2A CN201710492746A CN107090168A CN 107090168 A CN107090168 A CN 107090168A CN 201710492746 A CN201710492746 A CN 201710492746A CN 107090168 A CN107090168 A CN 107090168A
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- 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
- C08L2201/04—Antistatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
-
- 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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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a kind of anlistatig 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, 0.5 1.5 parts by weight benzothiazoles, 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 heat-resistant stability 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 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
Close function admirable, it is easy to process, due to the various advantages that it has, be 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 one is entered in terms of antistatic property, the transparency, heat resistance to PC/ABS composition articles
The demand of the raising of step.
The content of the invention
It is an object of the invention to a kind of anlistatig PC/ABS compositions and preparation method thereof, prepared using said composition
Product while with good mechanical properties, with excellent antistatic property, the transparency and heat-resistant stability.
Technical scheme is as follows：
A kind of anlistatig PC/ABS compositions, including：50-70 parts by weight PC, 10-20 parts by weight ABS, 3-15 parts by weight
The triblock copolymer of 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, 0.5-1.5 parts by weight benzothiazoles, 0.1-1 parts by weight antioxidant, and 0.5-2 parts by weight
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,
12- amido lauric acid/dodecanoic acids, terephthalic acid (TPA), antioxidant 1010, Yi Jishui, by hot pressing are inserted in autoclave
After replacing with nitrogen in reactor, in closed lower heating stirring 4-5 hour of 220-230 DEG C of pressurization (0.3~0.5MPa), two are obtained last
Polyamide of the end with 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.
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 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, benzothiazole, antioxidant and lubricant are weighed by weight ratio, are mixed
Uniformly, then by 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：210-230 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；Simultaneously product have good compatibility with
And the transparency.Benzothiophene is used in composition then so that composition article has good heat-resistant stability.
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 PC/ABS compositions particle is 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：Weigh by weight ratio polyether ester amides (or organic antistatic agentses a or b), inorganic antistatic agent, benzothiazole,
Antioxidant and lubricant, are well mixed, then it are added to together with the material that a steps are mixed in high-speed mixer and continue mixed
Close 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, 215 DEG C of 2nd area, 215 DEG C of 3rd area, 220 DEG C of 4th area, 5th area
230 DEG C, 230 DEG C of 6th area, 220 DEG C of 7th area, 210 DEG C of 8th area；Screw rod revolution is controlled in 300rpm；Residence time 8min.
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；Benzothiazole is from commercially available；Antioxidant is antioxidant 1010 and 168 with 1:1 weight
Than the mixture of 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 determines load deflection temperature (experiment chip size according to ASTM D-648 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 to test piece with (1) identical, washed and tilted with 100ml/ points of flow using 23 DEG C of ion exchange water 100ml
After the test film of placement, dried 3 hours with 80 DEG C of temperature in air circulation drying box.The step of washing-drying is repeated
After rapid 15 times, the test piece is stood 48 hours under conditions of 23 DEG C, humidity 50%RH, then with teraohmmeter in identical
It is measured under environment.
(3) specific insulation：Identical test film is tested using with surface resistivity, is measured in the same way
[according to ASTM D257].
The transparency：Mist degree is determined according to JIS K7105-1981.
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 heat-resistant stability, and
After it experienced water washing operations, still with good antistatic property.
And it is very few or during using other kinds of polyethers (ester) amide-type antistatic additive without using, usage amount, its is antistatic
Performance is decreased obviously, while when inorganic antistatic agent and above-mentioned polyethers (ester) amide-type organic antistatic agentses not being applied in combination,
The antistatic property of composition article is also reduced, and the surface resistivity after especially washing is significantly increased；Use other species
When organic antistatic agentses or very few compatilizer (triblock copolymer) consumption, its mist degree enhancing, transparency declines；Without using benzo
The composition article of thiazole, its heat resistance is decreased obviously.
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 (6)
1. a kind of anlistatig PC/ABS compositions, it is characterised in that including following component：50-70 parts by weight PC, 10-20 weight
Measure the triblock copolymer of part ABS, 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, 0.5-1.5 parts by weight benzothiazoles, 0.1-1 parts by weight
Antioxidant, and 0.5-2 parts by weight lubricants, wherein, polyether ester amides are made by the following method, are inserted in autoclave
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 pressurizations (0.3~0.5MPa) closed lower heating stirring 4-5 hours, obtaining two ends has the polyamide of carboxyl；Secondly add
Enter polyethylene glycol and zirconium acetate that number-average molecular weight is 500-1000, in poly- under 230-250 DEG C, below 0.12kPa decompression
4-6 hours are closed to obtain sticky polymer；This polymer granulate obtaining polyether ester to take out in thread on tape
Acid amides.
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. the preparation method of anlistatig 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, benzothiazole, antioxidant and lubricant are weighed by weight ratio, are well mixed,
It is added to together with the material that a steps are mixed again 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 |
|---|---|---|---|---|
| CN109852023A (en) * | 2018-12-17 | 2019-06-07 | 上海凯雄新材料科技有限公司 | A kind of fire retardation PC-ABS alloy building template |
| 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 |
| CN114516848A (en) * | 2022-02-11 | 2022-05-20 | 万华化学集团股份有限公司 | Preparation method of polycarbonate high-temperature degradation resistant agent and polycarbonate composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109852023A (en) * | 2018-12-17 | 2019-06-07 | 上海凯雄新材料科技有限公司 | A kind of fire retardation PC-ABS alloy building template |
| 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 |
| CN114516848A (en) * | 2022-02-11 | 2022-05-20 | 万华化学集团股份有限公司 | Preparation method of polycarbonate high-temperature degradation resistant agent and polycarbonate composition |
| CN114516848B (en) * | 2022-02-11 | 2024-02-02 | 万华化学集团股份有限公司 | Preparation method of polycarbonate high-temperature degradation resistant agent and polycarbonate composition |
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Application publication date: 20170825 |