CN110372988A - A kind of ABS/POK composite material and preparation method - Google Patents
A kind of ABS/POK composite material and preparation method Download PDFInfo
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- CN110372988A CN110372988A CN201910670165.2A CN201910670165A CN110372988A CN 110372988 A CN110372988 A CN 110372988A CN 201910670165 A CN201910670165 A CN 201910670165A CN 110372988 A CN110372988 A CN 110372988A
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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
-
- 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
-
- 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
-
- 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
- B29C2948/9259—Angular 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
- 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
-
- 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
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
Abstract
The invention discloses a kind of ABS/POK composite material, the ingredient comprising following parts by weight: 20-77.8 parts of ABS resin, 15-60 parts of POK polyketone resin, 5-30 parts of PETG resin.The invention is by POK polyketone resin and ABS alloy, the very good solution consistency technique bottleneck problem of resin system, greatly improve the mechanical property of material, PETG assigns the preferable glossiness of material simultaneously, POK resin imparts the excellent weatherability of material, solvent resistance, the deficiency of existing ABS alloy material is compensated for, there is biggish industrial application value.Meanwhile invention additionally discloses a kind of preparation methods of ABS/POK composite material.
Description
Technical field
The invention belongs to ABS composite material technical fields, and in particular to a kind of ABS/POK composite material and its preparation side
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.
But ABS material oil resistant, organic solvent resistance are poor, are then also easy to produce swelling simultaneously in nonpolar oil product or chemical solvent
There is breakage, unsaturated polybutadiene double bond coloured effect product appearance easy to aging, this performance deficiency greatly limit in structure
ABS material has been made in the application and popularization of some product scopes.ABS material is most sensitive for glacial acetic acid solvent, and product is once
It touches, generally can generate big crackle within 20 seconds so that fracture, therefore, the ABS material of resistance to glacial acetic acid solvent belongs at present
In the technical bottleneck problem of industry, once it solves that medical treatment, need of the industries such as energy for material solvent resistance can be met
It asks, expands potential application market, have compared with larger market prospect.
Summary of the invention
Based on this, it is multiple that a kind of ABS/POK is provided it is an object of the invention to overcome in place of above-mentioned the deficiencies in the prior art
Condensation material.The ABS/POK composite material has excellent high glaze, solvent resistant, weather resistance.
To achieve the above object, the technical solution adopted by the present invention are as follows: a kind of ABS/POK composite material, comprising following heavy
Measure the ingredient of part: 20-77.8 parts of ABS resin, 15-60 parts of POK polyketone resin, 5-30 parts of PETG resin.
The present invention by POK polyketone resin and ABS alloy, ask by the consistency technique bottleneck of very good solution resin system
Topic greatly improves the mechanical property of material, and PETG assigns the preferable glossiness of material, and it is excellent that POK resin imparts material
Weatherability, solvent resistance compensate for the deficiency of existing ABS alloy material, have biggish industrial application value.
Preferably, melt flow rate (MFR) of the POK polyketone resin under 240 DEG C, 2.16kg test condition is greater than 120g/
10min。
Preferably, shown in the structural formula such as formula (1) of the POK polyketone resin:
Wherein, 100 < m < 15000, n >=m+1.
Preferably, in the PETG resin, the mass percentage of 1,4-CHDM (CHDM) is no less than 50%
Then, poor using the alloy material glossiness and mechanical property of this resin exploitation.
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 ABS/POK composite material, also includes the compatilizer of 2-8 parts by weight, and the compatilizer is ABS
Grafted maleic anhydride, ABS grafted propylene acid methyl esters, in styrene-acrylonitrile-glycidyl methacrylate terpolymer
At least one.
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 ABS/POK composite material also includes the processing aid of 0.2-1 parts by weight.
Meanwhile the present invention also provides the preparation method of the ABS/POK 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 present invention by POK polyketone resin and ABS alloy, ask by the consistency technique bottleneck of very good solution resin system
Topic greatly improves the mechanical property of material, and PETG assigns the preferable glossiness of material, and it is excellent that POK resin imparts material
Weatherability, solvent resistance compensate for the deficiency of existing ABS alloy material, have biggish industrial application value.
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/POK composite material the preparation method comprises the following steps:
(1) ABS resin, POK polyketone resin, PETG resin, compatilizer and processing aid are subjected to high-speed stirring in proportion
Batch mixer is mixed to be uniformly mixed or enter 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, and the test of the performance is all first by composite material
It is prepared into the test carried out after test bars:
The measurement standard of each performance of table 1
The present invention is arranged Examples 1 to 8, each ingredient in specific embodiment 1~5, unless specific instructions, be it is commercially available can
: where ABS is commercially available ABS 8391；POK polyketone resin is commercially available POK M230A (100 < m < 15000, m > 1, n > m+
1)；PETG is the commercially available GN071 of U.S. Yi Shiman (mass percentage of 1,4-CHDM is less than 50%), processing aid
Including antioxidant, lubricant, specific antioxidant, lubricant weight ratio be 1:1, wherein antioxidant selects BASF
Irganox 1010 and Irganox 168, lubricant are selected from N, N'- ethylenebisstearamide (EBS)；In Examples 1 to 5
Compatilizer is respectively that ABS grafted maleic anhydride, ABS grafted propylene acid methyl esters, styrene-acrylonitrile-Glycidyl methacrylate are sweet
Grease terpolymer, styrene-acrylonitrile-glycidyl methacrylate terpolymer, styrene-acrylonitrile-first
Base glycidyl acrylate terpolymer, wherein styrene-acrylonitrile-glycidyl methacrylate terpolymer
Average particle size be 40-350 μm (according to ISO 13320:2009 standard, after sample dispersion be ultrasonically treated in water, using sharp
Light particle size analyzer is tested), epoxy content is 5 ± 0.2wt%, and weight average molecular weight is 1.4 × 105g/mol；In Examples 1 to 5
ABS resin be made of grafted polybutadiene rubber and grafted polystyrene-acrylonitrile copolymer, the grafted polybutadiene rubber
Glue 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, epoxy content, weight average molecular weight are different outer, other compositions and content with reality
Apply the average grain for the styrene-acrylonitrile-glycidyl methacrylate terpolymer that example 5 is identical, in specific embodiment 8
Spend 350 μm of > (according to ISO 13320:2009 standard, after sample dispersion is ultrasonically treated in water, using laser particle analyzer into
Row test), epoxy content is 4 ± 0.2wt%, weight average molecular weight 2.5 × 105g/mol.Each ingredient contains in specific embodiment 1~8
It measures (in parts by weight) and the performance test results is as shown in table 2:
Each component content and the performance test results in 2 Examples 1 to 8 of table
From table 2 it can be seen that ABS/POK composite material of the present invention has excellent solvent resistance, weather-proof, glossiness, it is whole
Body has excellent comprehensive mechanical property and volume production application value.Embodiment 6,7 and the comparison of embodiment 5 are found, when the poly- fourth of grafting
Diene rubber and grafted polystyrene-acrylonitrile copolymer weight ratio are (5~80): when (20~95), ABS/POK 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/POK composite material more excellent comprehensive performance (while having preferable
Tensile strength, impact strength, weatherability).
In addition, experimental group 1~6 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 8391；
POK polyketone resin: being that (melt index is > 120g/ to POK M930A in experimental group 1~5 and control group 1~3
10min, test condition are 240 DEG C/2.16kg), be in experimental group 6 POK M330A (melt index is 40~120g/10min,
Test condition is 240 DEG C/2.16kg)；
PETG resin is that (mass percentage of 1,4 cyclohexane dimethanol is less than the commercially available GN071 of U.S. Yi Shiman
50%)；
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), specific antioxidant, lubricant content weight ratio be 1:1.
Each component content and each the performance test results are as shown in table 3 in specific experiment group 1~6 and control group 1~3:
Each component content and each the performance test results in 3 experimental group 1~6 of table and control group 1~3
From table 3 it can be seen that ABS/POK composite material is whole in experimental group 1~6 of the present invention compared with control group 1~3
It is whole that there is excellent comprehensive mechanical property and volume production application value with excellent glossiness, solvent resistance and weatherability.It will be right
Find that POK resin improves the resistance to glacial acetic acid performance and weather resistance of material according to group 1 and the comparison of control group 2, control group 2 with it is right
It compares and finds according to group 3, compatilizer efficiently solves the compatibility of material, improves the impact strength of material；By control group 3 and in fact
Test 1 comparison of group, the addition of PETG resin greatly improves the glossiness and weatherability of material, experimental group 1 compared with experimental group 2,
The increase of POK content has been obviously prolonged cracking time of material under the conditions of glacial acetic acid, improves the resistance to glacial acetic acid cracking of material
Performance, experimental group 3,4,5 compare experimental group 2, and the melt flow rate (MFR) test result of material is continuously improved, by recording batten table
The time that face cracks does not crack after 30 minutes, and the resistance to glacial acetic acid ability of material greatly improves, while the xenon lamp of material
Aging color difference is sequentially reduced, and weatherability is continuously improved；Experimental group 6 and experimental group 5 are compared it is found that melting when POK polyketone resin
When melting index > 120g/10min, there is better tensile strength, impact strength, weatherability and glossiness, resistance to glacial acetic acid cracking
Time substantially extends, and the comprehensive performance tool of material improves a lot.
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 (9)
1. a kind of ABS/POK composite material, which is characterized in that the ingredient comprising following parts by weight: 20-77.8 parts of ABS resin,
15-60 parts of POK polyketone resin, 5-30 parts of PETG resin.
2. ABS/POK composite material as described in claim 1, which is characterized in that the POK polyketone resin 240 DEG C,
Melt flow rate (MFR) under 2.16kg test condition is greater than 120g/10min.
3. ABS/POK composite material as described in claim 1, which is characterized in that the structural formula such as formula of the POK polyketone resin
(1) shown in:
Wherein, 100 < m < 15000, n >=m+1.
4. ABS/POK composite material as described in claim 1, which is characterized in that in the PETG resin, Isosorbide-5-Nitrae-hexamethylene two
The mass percentage of methanol is less than 50%.
5. ABS/POK composite material as described in claim 1, which is characterized in that the ABS resin is by grafted polybutadiene rubber
Glue and grafted polystyrene-acrylonitrile copolymer composition, the grafted polybutadiene rubber and grafted polystyrene-acrylonitrile are total
The weight ratio of polymers is (5~80): (20~95).
6. ABS/POK composite material as claimed in any one of claims 1 to 5, 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.
7. ABS/POK composite material as claimed in claim 6, which is characterized in that the compatilizer is styrene-acrylonitrile-
Glycidyl methacrylate terpolymer, the styrene-acrylonitrile-glycidyl methacrylate ternary polymerization
The average particle size of object 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):
8. ABS/POK composite material as claimed in any one of claims 1 to 5, which is characterized in that also include 0.2-1 parts by weight
Processing aid.
9. a kind of preparation method of ABS/POK composite material as described in any one of claims 1 to 8, which is characterized in that described
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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Cited By (6)
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| CN111016361A (en) * | 2019-12-20 | 2020-04-17 | 无锡赢同新材料科技有限公司 | PC/POK composite material with multilayer structure and preparation method thereof |
| WO2021012189A1 (en) * | 2019-07-23 | 2021-01-28 | 金发科技股份有限公司 | Abs/pok composite material and preparation method therefor |
| CN114085487A (en) * | 2021-11-11 | 2022-02-25 | 宁波坚锋新材料有限公司 | MABS composite material and preparation method thereof |
| WO2022047027A1 (en) * | 2020-08-28 | 2022-03-03 | Avient Corporation | Polymer blends of aliphatic polyketone, acrylonitrile butadiene styrene, and flame retardant |
| WO2022047030A1 (en) * | 2020-08-28 | 2022-03-03 | Avient Corporation | Polymer blends of aliphatic polyketone and acrylonitrile butadiene styrene |
| CN114196157A (en) * | 2021-11-30 | 2022-03-18 | 金发科技股份有限公司 | AES/POK alloy material, preparation method and application |
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| CN114085487A (en) * | 2021-11-11 | 2022-02-25 | 宁波坚锋新材料有限公司 | MABS composite material and preparation method thereof |
| CN114196157A (en) * | 2021-11-30 | 2022-03-18 | 金发科技股份有限公司 | AES/POK alloy material, preparation method and application |
| CN114196157B (en) * | 2021-11-30 | 2023-11-14 | 金发科技股份有限公司 | AES/POK alloy material, preparation method and application |
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Application publication date: 20191025 |
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