CN110343382A - A kind of high-performance flame-resistant ABS composite material and preparation method - Google Patents
A kind of high-performance flame-resistant ABS composite material and preparation method Download PDFInfo
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- CN110343382A CN110343382A CN201910669304.XA CN201910669304A CN110343382A CN 110343382 A CN110343382 A CN 110343382A CN 201910669304 A CN201910669304 A CN 201910669304A CN 110343382 A CN110343382 A CN 110343382A
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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
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
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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
- C08L73/00—Compositions of macromolecular compounds obtained by reactions forming a linkage containing oxygen or oxygen and carbon in the main chain, not provided for in groups C08L59/00 - C08L71/00; Compositions of derivatives of such polymers
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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
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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Abstract
The invention discloses a kind of high-performance flame-resistant ABS composite material, the ingredient comprising following parts by weight: 28-73 parts of ABS resin, 5-50 parts of POK polyketone resin, melt index of the POK polyketone resin under 240 DEG C, 2.16kg test condition are greater than 120g/10min.The invention is by the POK polyketone resin of specific structure and ABS alloy, the very good solution consistency technique bottleneck problem of resin system, greatly improve the mechanical property of material, simultaneously because the advantages of POK resin itself, the features such as imparting the excellent weatherability of material, solvent resistance, heat resistance, the deficiency of existing flame-proof ABS alloy material is compensated for, there is biggish industrial application value.Meanwhile the present invention also provides a kind of preparation methods of high-performance flame-resistant ABS composite material.
Description
Technical field
The invention belongs to ABS composite material technical fields, and in particular to a kind of high-performance flame-resistant ABS composite material and its system
Preparation Method.
Background technique
The terpolymer that ABS resin is made of styrene, butadiene, acrylonitrile, with styrene high fluidity,
The toughness of butadiene and the chemical resistance corrosion characteristic of acrylonitrile have excellent processing performance, resistance to low temperature, electrical isolation
Performance, high glaze and excellent plating performance, while it is excellent to have that creep resistant is good, dimensional stability is high, molding shrinkage is small etc.
Different feature, it is very widely used in the plastic products in the fields such as household electrical appliances, automobile, electronic apparatus.
The oxygen index (OI) of ABS resin only has 18%, and glowing filament ignition temperature only has 700 DEG C or so, and vertical combustion can only achieve
HB grades, it is difficult to be tested by needle flame, these performance deficiencies cause it more difficult applied to some electric appliances with higher safety requirement
Product, only passage capacity are promoted, and are developed a kind of new flame-retarded technology, are assigned the higher flame retardant property of material, be just able to satisfy production
The performance requirements such as oxygen index (OI), glowing filament, the test of needle flame in product application.
Summary of the invention
Based on this, a kind of high-performance refractory is provided it is an object of the invention to overcome above-mentioned the deficiencies in the prior art place
ABS composite material.The ABS composite material has excellent heat resistance, weatherability, solvent resistance, wearability.
To achieve the above object, the technical solution adopted by the present invention are as follows: a kind of high-performance flame-resistant ABS composite material includes
The ingredient of following parts by weight: 28-73 parts of ABS resin, 5-50 parts of POK polyketone resin, the POK polyketone resin 240 DEG C,
Melt index under 2.16kg test condition is greater than 120g/10min, shown in the structural formula such as formula (1) of the POK polyketone resin:
Wherein, 100 < m < 15000, n >=m+1.
The invention by the POK polyketone resin of specific structure and ABS alloy, very good solution resin system
Consistency technique bottleneck problem greatly improves the mechanical property of material, simultaneously because imparting the advantages of POK resin itself
The features such as excellent weatherability of material, solvent resistance, heat resistance, compensates for the deficiency of existing flame-proof ABS alloy material, have compared with
Big industrial application value.
Preferably, the high-performance flame-resistant ABS composite material also includes the ingredient of following parts by weight: ABS resin 35-
70 parts, 15-50 parts of POK polyketone resin.
Preferably, the ABS resin is made of grafted polybutadiene rubber and grafted polystyrene-acrylonitrile copolymer,
The grafted polybutadiene rubber and grafted polystyrene-acrylonitrile copolymer weight ratio are (5~80): (20~95).ABS
Resin can be synthesized by substance law or emulsion method, can also be by grafted polybutadiene rubber and acrylonitrile-polystyrene copolymer
It is blended and obtains.
Preferably, the high-performance flame-resistant ABS composite material also includes the ingredient of following parts by weight: bromide fire retardant
13-17 parts, 3-7 parts of Sb system fire retardant.
It is highly preferred that the bromide fire retardant is decabromodiphenylethane, brominated epoxy resin, brominated Polystyrene, tetrabromo
At least one of bisphenol-A and three (tribromo phenyl) triazines, bromination imines；The Sb system fire retardant is antimony oxide, five oxygen
Change at least one of two antimony, sodium antimonate, phosphoric acid antimony.
Preferably, the high-performance flame-resistant ABS composite material also includes the compatilizer of 2-8 parts by weight, the compatilizer
It is total for ABS grafted maleic anhydride, ABS grafted propylene acid methyl esters, styrene-acrylonitrile-glycidyl methacrylate ternary
At least one of polymers.
It is highly preferred that the compatilizer is styrene-acrylonitrile-glycidyl methacrylate terpolymer, institute
The average particle size for stating styrene-acrylonitrile-glycidyl methacrylate terpolymer is 40-350 μm, and epoxy content is
4-6wt%, weight average molecular weight 1.0 × 105g/mol-3.0×105G/mol, shown in structural formula such as formula (2):
Granularity is smaller to be also easy to produce reunion, and the excessive compatibilization effect of granularity reduces, and epoxy content is related to increase-volume efficiency, molecular weight
Size is related to mechanical property.
Preferably, the high-performance flame-resistant ABS composite material also includes the processing aid of 0.2-2 parts by weight.
Preferably, the high-performance flame-resistant ABS composite material also includes the weather resisting agent of 0.1-1 parts by weight, described weather-proof
Agent is the compounding of benzotriazole light stabilizer, hindered amine light stabilizer.
It is highly preferred that the benzotriazole light stabilizer is at least one of compound A, compound B, the chemical combination
Shown in the structural formula of object A such as formula (3), shown in the structural formula such as formula (4) of the compound B；The hindered amine light stabilizer
Shown in structural formula such as formula (5):
Meanwhile the present invention also provides the preparation method of the high-performance flame-resistant ABS composite material described in one kind, the methods
Are as follows:
(1) each ingredient is uniformly mixed in high-speed stirred batch mixer or enters twin-screw separately through metering feeding device and squeezed
Out in machine；
(2) under the conveying of double screw extruder, mixing and shear action, the abundant fusion plastification of each ingredient in formula is pinched
It closes and is kneaded, through head extrusion, tie rod, cooling, pelletizing, drying, packaging, obtain the novel environment friendly flame-retardant ABS compound material；Its
In, each section of extruder temperature of double screw extruder is respectively as follows: 80 DEG C of an area, 160 DEG C of 2nd area, three areas 180 from feed opening to head
DEG C, 230 DEG C of 4th area, 230 DEG C of 5th area, 230 DEG C of 6th area, 220 DEG C of 7th area, 220 DEG C of 8th area, 220 DEG C of 9th area, 230 DEG C of head, screw rod
Revolving speed is 300-400rpm, and the draw ratio of double screw extruder is 40:1.
The above-mentioned preparation method process of the present invention is simple, continuous, high production efficiency, product with stable quality.
Compared with the existing technology, the invention has the benefit that
The POK polyketone resin of specific structure and ABS alloy are efficiently solved conventional two kinds of trees by the invention
The consistency technique bottleneck problem of rouge, is prepared for a kind of alloy material of high performance, has preferable heat resistance, solvent resistance
Energy, weather resistance, wear-resisting property etc., and the easy use that fire retardant can be reduced at charcoal of the POK polyketone of specific structure itself
Amount, belongs to a kind of novel green polymer, so that the alloy material of preparation has unique environmentally protective characteristic, technical side's mask
There are very big originality, simple production process, convenient for industrialization scale of mass production.
Specific embodiment
To better illustrate the object, technical solutions and advantages of the present invention, below in conjunction with specific embodiment to the present invention
It is described further.
In the embodiment of the present invention ABS composite material the preparation method comprises the following steps:
(1) by ABS resin, POK polyketone resin, bromide fire retardant, Sb system fire retardant, compatilizer and processing aid press than
Example carries out high-speed stirred batch mixer and is uniformly mixed or enters in double screw extruder separately through metering feeding device；
(2) under the conveying of double screw extruder, mixing and shear action, the abundant fusion plastification of each ingredient in formula is pinched
It closes and is kneaded, through head extrusion, tie rod, cooling, pelletizing, drying, packaging, obtain the novel high-performance flame-retardant ABS compound material；
Wherein, each section of extruder temperature of double screw extruder is respectively as follows: 80 DEG C of area's temperature, two area's temperature 160 from feed opening to head
DEG C, 180 DEG C of three area's temperature, 230 DEG C of four area's temperature, 230 DEG C of five area's temperature, 230 DEG C of six area's temperature, 220 DEG C of seven area's temperature, 8th area
220 DEG C of temperature, 220 DEG C of nine area's temperature, 230 DEG C of head temperature, screw speed are preferably 320rpm, the major diameter of double screw extruder
Than for 40:1.
The specific evaluation method of each performance is as shown in table 1 in embodiment:
The measurement standard of each performance of table 1
| Detection project | Unit | Execution standard |
| Tensile strength | MPa | ISO527 |
| Izod notched impact strength | kJ/m2 | ISO180 |
| Flame retardant property | Class | UL 94 |
| Heat distortion temperature | ℃ | ASTM D648 |
| Weatherability | % | ISO 4893-2/200h |
Examples 1 to 10 is arranged in the present invention, and each ingredient in specific embodiment 1~5 is unless specific instructions commercially available
It can obtain: where ABS is commercially available ABS PA-757K；POK polyketone resin is commercially available POK M930A (100 < m < 15000, n >=m+
1, melt index is > 120g/10min)；Bromide fire retardant is decabromodiphenylethane, selects the product STYTEX of refined precious bromine
8010；Sb system fire retardant is selected from Changde Chen Zhou product Sb2O3；Processing aid includes antioxidant, lubricant and anti-dripping agent, specifically
The weight ratio of the content of antioxidant, lubricant, anti-dripping agent is 1:1:0.5, and wherein antioxidant selects the Irganox of BASF
1010 and Irganox 168, lubricant are selected from N, N'- ethylenebisstearamide (EBS), and anti-dripping agent is selected from X-010, weather-proof
Agent is TINUVIN 234 (benzotriazole light stabilizer) and UV-770 (hindered amine light stabilizer) is combined；Examples 1 to 5
In compatilizer be respectively ABS grafted maleic anhydride, ABS grafted propylene acid methyl esters, the contracting of styrene-acrylonitrile-methacrylic acid
Water glyceride terpolymer, styrene-acrylonitrile-glycidyl methacrylate terpolymer, styrene-propene
Nitrile-glycidyl methacrylate terpolymer, wherein styrene-acrylonitrile-glycidyl methacrylate ternary
The average particle size of copolymer is 40-350 μm, and when epoxy content is 5 ± 0.2wt%, weight average molecular weight is 1.4 × 105g/mol；
ABS resin in Examples 1 to 5 is made of grafted polybutadiene rubber and grafted polystyrene-acrylonitrile copolymer, described to connect
Branch polybutadiene rubber and grafted polystyrene-acrylonitrile copolymer weight ratio are successively are as follows: 5:95,80:20,40:60,50:
50,28:72.
Except grafted polybutadiene rubber and grafted polystyrene-acrylonitrile copolymer weight ratio and reality in embodiment 6,7
It is different outer to apply example 5, other compositions and content are same as Example 5, and grafted polybutadiene rubber and grafting are poly- in embodiment 6,7
The weight ratio of styrene-acrylonitrile copolymer is respectively 2:98,85:15；Styrene-acrylonitrile-methacrylic acid in embodiment 8
The average particle size of ethylene oxidic ester terpolymer, density, epoxy content are different outer, other compositions and content with embodiment 5
It is identical, the average particle size > of the styrene-acrylonitrile-glycidyl methacrylate terpolymer in specific embodiment 8
350 μm, epoxy content is 4 ± 0.2wt%, weight average molecular weight 2.5 × 105g/mol；In embodiment 9,10 not except weather resisting agent selection
With outside, other are in the same manner as in Example 5, and weather resisting agent is respectively that (benzotriazole light is steady by TINUVIN 234 in embodiment 9,10
Determine agent), UV-770 (hindered amine light stabilizer).Each component content and the performance test results such as table 2 in specific embodiment 1~10
It is shown:
Each component content and the performance test results in 2 Examples 1 to 10 of table
From table 2 it can be seen that ABS composite material of the present invention has excellent heat resistance, solvent resistance and weather-proof, anti-flammability
Can, it is whole that there is excellent comprehensive mechanical property and volume production application value.Embodiment 6,7 and the comparison of embodiment 5 are found, grafting is worked as
Polybutadiene rubber and grafted polystyrene-acrylonitrile copolymer weight ratio are (5~80): when (20~95), ABS composite wood
Material has more preferable comprehensive performance；Embodiment 8 and the comparison of embodiment 5 are found, when styrene-acrylonitrile-Glycidyl methacrylate
In glyceride terpolymer average particle size be 40-350 μm, epoxy content be 4-6wt% when, weight average molecular weight be 1.0 ×
105g/mol-3.0×105When g/mol, there is ABS composite material more excellent comprehensive performance (while having preferable stretching
Intensity, impact strength, weatherability)；Embodiment 9,10 and the comparison of embodiment 5 are found, when weather resisting agent selects TINUVIN 234
When the compounding of (benzotriazole light stabilizer) and UV-770 (hindered amine light stabilizer), ABS composite material of the present invention
With better weatherability, color difference is smaller after xenon lamp aging.
In addition, experimental group 1~7 and control group 1~3 is arranged in the present invention, specific experimental group and control group of the invention are used
The following raw material, but it is not limited only to these raw materials:
ABS resin: being made of grafted polybutadiene rubber and grafted polystyrene-acrylonitrile copolymer, and the grafting is poly-
Butadiene rubber and grafted polystyrene-acrylonitrile copolymer weight ratio are (5~80): (20~95), such as ABS PA-
757K；
POK polyketone resin: POK M930A (melt index is > 120g/10min, and test condition is 240 DEG C/2.16kg),
POK M330A (melt index is 40~120g/10min, and test condition is 240 DEG C/2.16kg)；
Bromide fire retardant: decabromodiphenylethane selects the product STYTEX 8010 of the bromine of refined treasured；
Sb system fire retardant: it is selected from Changde Chen Zhou product Sb2O3；
Compatilizer: good easy appearance SAG-002 (put down by styrene-acrylonitrile-glycidyl methacrylate terpolymer
Equal granularity is 40-350 μm, and when epoxy content is 5 ± 0.2wt%, weight average molecular weight is 1.4 × 105g/mol)；
Processing aid: antioxidant selects the Irganox 1010 and Irganox 168 of BASF, and lubricant is selected from N, N'-
Ethylenebisstearamide (EBS), polytetrafluoroethylene (PTFE) anti-dripping agent X-010, specific antioxidant, lubricant, anti-dripping agent contain
The weight ratio of amount is 1:1:0.5.
Weather resisting agent: TINUVIN 234 (benzotriazole light stabilizer) and UV-770 (hindered amine light stabilizer) are answered
Match.
Each component content and each the performance test results are as shown in table 3 in specific experiment group 1~7 and control group 1~3:
Each component content and each the performance test results in 3 experimental group 1~7 of table and control group 1~3
From table 3 it can be seen that experimental group 1 and control group 1~2 are compared it is found that the specific POK polyketone resin of the present invention adds
Enter, heat distortion temperature and weatherability can be improved；By experimental group 2 compared with control group 3, the addition of POK polyketone resin be can be improved
The weatherability of material, and since POK polyketone resin itself has preferably at charcoal, the increase of content can be improved fire-retardant etc.
Grade.By experimental group 5,6,7 compared with experimental group 4, with further increasing for POK polyketone resin content, the heat resistance of material and
Weatherability further increases；By experimental group 3 compared with experimental group 4, compatilizer styrene-acrylonitrile-methyl of the present invention
Glycidyl acrylate terpolymer improves the impact property of system, meets the toughness requirements of material application aspect.
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention rather than protects to the present invention
The limitation of range is protected, although the invention is described in detail with reference to the preferred embodiments, those skilled in the art should
Understand, it can be with modification or equivalent replacement of the technical solution of the present invention are made, without departing from the essence of technical solution of the present invention
And range.
Claims (10)
1. a kind of high-performance flame-resistant ABS composite material, which is characterized in that the ingredient comprising following parts by weight: ABS resin 28-73
Part, 5-50 parts of POK polyketone resin, melt index of the POK polyketone resin under 240 DEG C, 2.16kg test condition is greater than
120g/10min, shown in the structural formula such as formula (1) of the POK polyketone resin:
Wherein, 100 < m < 15000, n >=m+1.
2. high-performance flame-resistant ABS composite material as described in claim 1, which is characterized in that the ABS resin is by being grafted poly- fourth
Diene rubber and grafted polystyrene-acrylonitrile copolymer composition, the grafted polybutadiene rubber and grafted polystyrene-the third
The weight ratio of alkene lonitrile copolymer is (5~80): (20~95).
3. high-performance flame-resistant ABS composite material as claimed in claim 1 or 2, which is characterized in that also comprising following parts by weight
Ingredient: 13-17 parts of bromide fire retardant, 3-7 parts of Sb system fire retardant.
4. high-performance flame-resistant ABS composite material as claimed in claim 3, which is characterized in that the bromide fire retardant is ten bromines
In diphenylethane, brominated epoxy resin, brominated Polystyrene, tetrabromobisphenol A and three (tribromo phenyl) triazines, bromination imines extremely
Few one kind；The Sb system fire retardant is at least one of antimony oxide, antimony pentoxide, sodium antimonate, phosphoric acid antimony.
5. high-performance flame-resistant ABS composite material as claimed in claim 1 or 2, which is characterized in that also comprising 2-8 parts by weight
Compatilizer, the compatilizer are ABS grafted maleic anhydride, ABS grafted propylene acid methyl esters, styrene-acrylonitrile-methacrylic acid
At least one of ethylene oxidic ester terpolymer.
6. high-performance flame-resistant ABS composite material as claimed in claim 5, which is characterized in that the compatilizer is styrene-the third
Alkene nitrile-glycidyl methacrylate terpolymer, the styrene-acrylonitrile-glycidyl methacrylate three
The average particle size of membered copolymer is 40-350 μm, epoxy content 4-6wt%, weight average molecular weight 1.0 × 105g/mol-3.0×
105G/mol, shown in structural formula such as formula (2):
7. high-performance flame-resistant ABS composite material as claimed in any one of claims 1 to 3, which is characterized in that also include 0.2-2
The processing aid of parts by weight.
8. high-performance flame-resistant ABS composite material as claimed in any one of claims 1 to 3, which is characterized in that also include 0.1-1
The weather resisting agent of parts by weight, the weather resisting agent are the compounding of benzotriazole light stabilizer, hindered amine light stabilizer.
9. high-performance flame-resistant ABS composite material as claimed in claim 8, which is characterized in that the benzotriazole light is stablized
Agent is at least one of compound A, compound B, shown in the structural formula such as formula (3) of the compound A, the compound B's
Shown in structural formula such as formula (4)；Shown in the structural formula of the hindered amine light stabilizer such as formula (5):
10. a kind of preparation method of high-performance flame-resistant ABS composite material as described in any one of claims 1 to 9, feature exist
In the method are as follows:
(1) each ingredient is uniformly mixed in high-speed stirred batch mixer or enters double screw extruder separately through metering feeding device
In；
(2) under the conveying of double screw extruder, mixing and shear action, the abundant fusion plastification of each ingredient in formula, mediate it is mixed
It refines, through head extrusion, tie rod, cooling, pelletizing, drying, packaging, obtains the high-performance flame-resistant ABS composite material；Wherein, double
Each section of extruder temperature of screw extruder is respectively as follows: 80 DEG C of an area, 160 DEG C of 2nd area, 180 DEG C of 3rd area, four from feed opening to head
230 DEG C of area, 230 DEG C of 5th area, 230 DEG C of 6th area, 220 DEG C of 7th area, 220 DEG C of 8th area, 220 DEG C of 9th area, 230 DEG C of head, screw speed
For 300-400rpm, the draw ratio of double screw extruder is 40:1.
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| CN111363298A (en) * | 2020-03-27 | 2020-07-03 | 暨南大学 | Antibacterial solvent-resistant sphygmomanometer shell material and preparation method and application thereof |
| CN112266568A (en) * | 2020-10-19 | 2021-01-26 | 武汉金发科技有限公司 | High-shrinkage ABS resin composition and preparation method thereof |
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| WO2022047030A1 (en) * | 2020-08-28 | 2022-03-03 | Avient Corporation | Polymer blends of aliphatic polyketone and acrylonitrile butadiene styrene |
| WO2022047027A1 (en) * | 2020-08-28 | 2022-03-03 | Avient Corporation | Polymer blends of aliphatic polyketone, acrylonitrile butadiene styrene, and flame retardant |
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