CN105860479A - Low-precipitation high-performance flame-retardant PC/ABS (polycarbonate/acrylonitrile-butadiene-styrene) composition - Google Patents
Low-precipitation high-performance flame-retardant PC/ABS (polycarbonate/acrylonitrile-butadiene-styrene) composition Download PDFInfo
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- CN105860479A CN105860479A CN201610272319.9A CN201610272319A CN105860479A CN 105860479 A CN105860479 A CN 105860479A CN 201610272319 A CN201610272319 A CN 201610272319A CN 105860479 A CN105860479 A CN 105860479A
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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
-
- 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
- B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
-
- 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
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
-
- 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
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2055/00—Use of specific polymers obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of main groups B29K2023/00 - B29K2049/00, e.g. having a vinyl group, as moulding material
- B29K2055/02—ABS polymers, i.e. acrylonitrile-butadiene-styrene polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2069/00—Use of PC, i.e. polycarbonates or derivatives thereof, as moulding material
-
- 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
-
- 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
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a low-precipitation high-performance flame-retardant PC/ABS (polycarbonate/acrylonitrile-butadiene-styrene graft copolymer) composition which comprises PC, a phosphorus-containing flame retardant, ABS and a toughening modifier. The preparation method comprises the following steps: preparing a one-step material from the ABS and toughening modifier by physical extrusion, and mixing the one-step material with the rest materials to prepare the PC/ABS composition. The preparation method has the advantages of simple and accessible one-step material, simple preparation technique and low cost, can effectively remove small-molecule substances in the material molecules, and can obviously enhance the mechanical properties of the material. The material can be used in automobiles, refrigerators, televisions and other industries.
Description
Technical field
The invention belongs to macromolecule modified technical field, particularly relate to a kind of low precipitation high-performance refractory PC/ABS compositions.
Background technology
Merlon (PC) is a kind of thermoplastic engineering plastic with desirable physical mechanical performance, and it is transparent and fire-retardant
Property is excellent, has wide application；But owing to Merlon (PC) strand rigidity is big, melt viscosity is high, easily
Producing stress cracking, solvent resistance is poor, meets the shortcomings such as water easily decomposition under high temperature, limits it to a certain extent and uses model
Enclose.General by modification technology, improve it by the addition of acrylonitrile-butadiene-phenylethene grafted copolymer (ABS) and add
Work and internal stress, add impact improving agent and improve the toughness of Merlon (PC) compositions.But due to acrylonitrile-
Butadiene-styrene graft copolymer (ABS) and toughness reinforcing improving agent, when synthesis, can introduce dispersant or other auxiliary agents,
After making fire retardation PC/ABS compositions, due to the feature of Merlon (PC) molecular structure, these small-molecule substances can draw
Playing the degraded of Merlon (PC), small-molecule substance the most easily separates out simultaneously, thus the defect such as spray and residual mold deposit,
Have a strong impact on the outward appearance of product and the continuous production of product.
Summary of the invention
Present invention aim at providing a kind of low precipitation high-performance refractory PC/ABS compositions, said composition passes through a step material
Preparation, injection moulding process can be significantly reduced and produce spray and the chance of mold deposit.
The present invention finds under study for action, by the production of a step material, by it with fire retardant, Merlon (PC) suitably
The collocation of ratio, can effectively solve acrylonitrile-butadiene-phenylethene grafted copolymer (ABS) and anti-impact modifier
The problems such as spray that small molecular material causes and film dirt, significantly improve the outward appearance of product, improve material property simultaneously.Its
The concrete technical scheme used is as follows:
A kind of low precipitation high-performance refractory PC/ABS compositions, including Merlon (PC), phosphonium flame retardant, propylene
Nitrile-butadiene-styrene graft copolymer (ABS), plasticized modifier, first by acrylonitrile-butadiene-styrene (ABS) grafting altogether
Polymers (ABS) makes a step material with plasticized modifier by the method that physics is extruded, then is mixed with leftover materials by a step material
Close and prepare.
Further, the number-average molecular weight of described Merlon (PC), between 20000-40000, preferably exists
Between 25000-37000.
Further, described acrylonitrile-butadiene-phenylethene grafted copolymer (ABS) selects emulsion method or substance law to prepare
Acrylonitrile-butadiene-phenylethene grafted copolymer (ABS).
Further, described plasticized modifier uses MBS graft copolymer (MBS),
Core is organosilicon/acrylic acid, and shell is the silicon system anti-impact modifier of the nucleocapsid structure of methyl methacrylate.
Further, described phosphonium flame retardant is bisphenol-A bis phosphoric acid diphenyl ester (BDP), the double diphenylphosphoric acid of resorcinol
The mixture of one or more in ester (RDP) or triphenyl phosphate (TPP).
Further, in described compositions, Merlon (PC) accounts for 50-90%, phosphonium flame retardant by weight percentage
Account for 5-25%, a step material accounts for 5-35%.
Further, in described compositions, Merlon (PC) accounts for 60-80%, phosphonium flame retardant by weight percentage
Account for 9-15%, a step material accounts for 7-25%.
Further, in a described step material, acrylonitrile-butadiene-phenylethene grafted copolymer (ABS) by weight percentage
Account for 50%-80%, anti-impact modifier accounts for 20%-50%.
Further, the production method of a described step material is:
(1) by weight percentage acrylonitrile-butadiene-phenylethene grafted copolymer (ABS), plasticized modifier are put into height
Uniformly mix 1-3min, mix homogeneously in mixed machine, obtain premix material；
(2) premix material is put into from the main spout of double screw extruder, described in the condition that melt extrudes be: district's temperature
180-210 DEG C, two district's temperature 190-220 DEG C, three district's temperature 190-230 DEG C, four district's temperature 190-240 DEG C, five district's temperature
190-240 DEG C, six district's temperature 190-240 DEG C, seven district's temperature 190-240 DEG C, eight district's temperature 190-240 DEG C, nine district's temperature
190-240 DEG C, ten district's temperature 190-240 DEG C, 11 district's temperature 190-240 DEG C, engine speed 250-600 rev/min,
Preparing a step material plastic grain, the screw slenderness ratio of described double screw extruder is 48:1；
In (3) one step material production processes, it is 5%-30% liquid in the 3rd district of barrel and the 5th district implantation quality mark respectively
Water, SECTOR-SEVEN and the tenth district at barrel arrange double vacuum equipment simultaneously.
The present invention is by the extrusion of a step material, owing to aqueous water at high temperature volatilizees, dissolve take out of acrylonitrile-butadiene-
Small-molecule substance in phenylethene grafted copolymer (ABS) and plasticized modifier, coordinates the effect of double vacuum simultaneously, has
Effect volatile matter is taken out of barrel, produce and obtain a step material, produced to dry and re-use；The method can be effectively by third
Alkene nitrile-butadiene-styrene graft copolymer (ABS) separates with the small-molecule substance of plasticized modifier, particularly acrylonitrile
The alkalescence dispersant added in-butadiene-styrene graft copolymer (ABS) and plasticized modifier building-up process, so
The degraded of Merlon in modifying process (PC) can be prevented effectively from, little point during subsequent forming can be prevented effectively from simultaneously
The problems such as sub-material precipitation；Due to detaching of step material small-molecule substance in process of production, improve to a certain extent
The fire resistance of material.
The invention has the beneficial effects as follows: the step material that the present invention uses is simple and easy to get, preparation technology is simple, low cost, energy
While effectively removing material molecule small molecular material, the mechanical performance of material can be significantly improved again；Material can be used for
Automobile, refrigerator, the industry such as television set.
Detailed description of the invention
For the technological means making the present invention realize, creation characteristic, reach purpose and be easy to understand with effect, below to this
The detailed description of the invention of invention is described further, but does not limit protection scope of the present invention, it should be noted that not
In the case of conflict, the embodiment in the invention and the feature in embodiment can be mutually combined.
Embodiment 1:
One of the present invention low precipitation high-performance refractory PC/ABS compositions, first prepares a step material, first will be by weight
The amount ABS of 60% of percentages, the anti-impact modifier MBS of 40% uniformly mix 1-3min in high mixer,
To premix material；According to the method for the invention, premix material is put into double screw extruder, prepare a step material plastic grain.Press
PC described in percentage by weight meter accounts for 69.3%, and a step material accounts for 18%, and BDP accounts for 12%, and other auxiliary agents account for 0.7%,
Other auxiliary agents described include antioxidant and anti-dripping agent, and by the method for the invention, above-mentioned material is prepared low precipitation high-performance
Fire retardation PC/ABS compositions.
Embodiment 2:
One of the present invention low precipitation high-performance refractory PC/ABS compositions, first prepares a step material, first will be by weight
The amount ABS of 60% of percentages, the anti-impact modifier MBS of 40% uniformly mix 1-3min in high mixer,
To premix material；According to the method for the invention, premix material is put into double screw extruder, prepare a step material plastic grain.Press
PC described in percentage by weight meter accounts for 79.3%, and a step material accounts for 12%, and BDP accounts for 8%, and other auxiliary agents account for 0.7%, institute
State other auxiliary agents and include antioxidant and anti-dripping agent, above-mentioned material is prepared the resistance of low precipitation high-performance by the method for the invention
Combustion PC/ABS compositions.
Embodiment 3:
One of the present invention low precipitation high-performance refractory PC/ABS compositions, first prepares a step material, first will be by weight
The amount ABS of 60% of percentages, the anti-impact modifier MBS of 40% uniformly mix 1-3min in high mixer,
To premix material；According to the method for the invention, premix material is put into double screw extruder, prepare a step material plastic grain.Press
PC described in percentage by weight meter accounts for 59.3%, and a step material accounts for 25%, and BDP accounts for 15%, and other auxiliary agents account for 0.7%,
Other auxiliary agents described include antioxidant and anti-dripping agent, and by the method for the invention, above-mentioned material is prepared low precipitation high-performance
Fire retardation PC/ABS compositions.
Comparative example 1:
A kind of PC/ABS compositions with compositions of the present invention contrast, PC by weight percentage accounts for 69.3%,
ABS accounts for 10.8%, and MBS accounts for 7.2%, and BDP accounts for 12%, and other auxiliary agents account for 0.7%, and other auxiliary agents described include resisting
Oxygen agent and anti-dripping agent, be blended above material, prepares a kind of PC/ABS compositions.
Comparative example 2:
A kind of PC/ABS compositions with compositions of the present invention contrast, PC by weight percentage accounts for 79.3%,
ABS accounts for 7.2%, and MBS accounts for 4.8%, and BDP accounts for 8%, and other auxiliary agents account for 0.7%, and other auxiliary agents described include antioxygen
Agent and anti-dripping agent, be blended above material, prepares a kind of PC/ABS compositions.
Comparative example 3:
A kind of PC/ABS compositions with compositions of the present invention contrast, PC by weight percentage accounts for 59.3%,
ABS accounts for 15%, and MBS accounts for 10%, and BDP accounts for 15%, and other auxiliary agents account for 0.7%, and other auxiliary agents described include antioxygen
Agent and anti-dripping agent, be blended above material, prepares a kind of PC/ABS compositions.
To above example 1, embodiment 2, embodiment 3, comparative example 1, comparative example 2, comparative example 3, described PC/ABS
Compositions carries out performance test:
Mold deposit evaluation methodology: the square plate of injection 40*60*2mm, injection 100 moulds, can scrape off from fixing air vent continuously
Mold deposit weight.
Hot strength: testing standard ASTM D638, tests on Zwick electronic universal tester；
Izod notched impact: testing standard ASTM D256, tests on Zwick electronic universal tester；
Flame retardant rating: testing standard UL94.
Table 1PC/ABS composition properties test result
It can be seen that use the formula of a step material from table 1 result, the chance producing mold deposit can be significantly reduced, simultaneously
Mechanical property and fire resistance are more preferable.The addition of other auxiliary agents can more effectively improve the every of compositions
Performance, but be added without other auxiliary agents and have no effect on the technique effect of compositions of the present invention.
PC/ABS compositions of the present invention is described by specific embodiment.Those skilled in the art can
Suitably changing the link such as composition components, proportioning with reference present disclosure and realize other purpose corresponding, it is correlated with
Change all without departing from present disclosure, within all spirit in the invention and principle, any amendment of being made,
Equivalent, improvement etc., within should be included in the protection domain of the invention.
Claims (9)
1. a low precipitation high-performance refractory PC/ABS compositions, including Merlon, phosphonium flame retardant, acrylic nitrile-butadiene two
Alkene-phenylethene grafted copolymer, plasticized modifier, it is characterised in that first by acrylonitrile-butadiene-styrene (ABS) graft copolymerization
Thing makes a step material with plasticized modifier by the method that physics is extruded, then is mixed to prepare with leftover materials by a step material.
One the most according to claim 1 low precipitation high-performance refractory PC/ABS compositions, it is characterised in that described
The number-average molecular weight of Merlon is between 20000-40000, preferably between 25000-37000.
One the most according to claim 1 low precipitation high-performance refractory PC/ABS compositions, it is characterised in that described
The acrylonitrile-butadiene-styrene (ABS) that acrylonitrile-butadiene-phenylethene grafted copolymer selects emulsion method or substance law to prepare connects
Graft copolymer.
One the most according to claim 1 low precipitation high-performance refractory PC/ABS compositions, it is characterised in that described
Plasticized modifier uses MBS graft copolymer, and core is organosilicon/acrylic acid, and shell is
The silicon system anti-impact modifier of the nucleocapsid structure of methyl methacrylate.
One the most according to claim 1 low precipitation high-performance refractory PC/ABS compositions, it is characterised in that described
Phosphonium flame retardant be the one in bisphenol-A bis phosphoric acid diphenyl ester, the double diphenyl phosphoester of resorcinol or triphenyl phosphate or
Several mixture.
One the most according to claim 1 low precipitation high-performance refractory PC/ABS compositions, it is characterised in that described
In compositions, Merlon accounts for 50-90% by weight percentage, phosphonium flame retardant accounts for 5-25%, a step material accounts for 5-35%.
One the most according to claim 1 low precipitation high-performance refractory PC/ABS compositions, it is characterised in that described
In compositions, Merlon accounts for 60-80% by weight percentage, phosphonium flame retardant accounts for 9-15%, a step material accounts for 7-25%.
One the most according to claim 1 low precipitation high-performance refractory PC/ABS compositions, it is characterised in that described
In one step material, acrylonitrile-butadiene-phenylethene grafted copolymer by weight percentage accounts for 50%-80%, impact modification
Agent accounts for 20%-50%.
One the most according to claim 1 low precipitation high-performance refractory PC/ABS compositions, it is characterised in that described
The production method of one step material is:
(1) by weight percentage acrylonitrile-butadiene-phenylethene grafted copolymer, plasticized modifier are put in high mixer uniform
Mixing 1-3min, mix homogeneously, obtain premix material；
(2) premix material is put into from the main spout of double screw extruder, described in the condition that melt extrudes be: district's temperature
180-210 DEG C, two district's temperature 190-220 DEG C, three district's temperature 190-230 DEG C, four district's temperature 190-240 DEG C, five district's temperature
190-240 DEG C, six district's temperature 190-240 DEG C, seven district's temperature 190-240 DEG C, eight district's temperature 190-240 DEG C, nine district's temperature
190-240 DEG C, ten district's temperature 190-240 DEG C, 11 district's temperature 190-240 DEG C, engine speed 250-600 rev/min,
Preparing a step material plastic grain, the screw slenderness ratio of described double screw extruder is 48:1；
In (3) one step material production processes, it is 5%-30% aqueous water in the 3rd district of barrel and the 5th district implantation quality mark respectively,
SECTOR-SEVEN and the tenth district at barrel arrange double vacuum equipment simultaneously.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610272319.9A CN105860479A (en) | 2016-04-27 | 2016-04-27 | Low-precipitation high-performance flame-retardant PC/ABS (polycarbonate/acrylonitrile-butadiene-styrene) composition |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610272319.9A CN105860479A (en) | 2016-04-27 | 2016-04-27 | Low-precipitation high-performance flame-retardant PC/ABS (polycarbonate/acrylonitrile-butadiene-styrene) composition |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101173090A (en) * | 2006-10-31 | 2008-05-07 | 佛山市顺德区汉达精密电子科技有限公司 | PC/ABS alloy |
| CN102325827A (en) * | 2009-02-19 | 2012-01-18 | 拜尔材料科学股份公司 | Compounding process to produce polymer compositions having reduced levels of volatile organic compounds |
-
2016
- 2016-04-27 CN CN201610272319.9A patent/CN105860479A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101173090A (en) * | 2006-10-31 | 2008-05-07 | 佛山市顺德区汉达精密电子科技有限公司 | PC/ABS alloy |
| CN102325827A (en) * | 2009-02-19 | 2012-01-18 | 拜尔材料科学股份公司 | Compounding process to produce polymer compositions having reduced levels of volatile organic compounds |
Non-Patent Citations (2)
| Title |
|---|
| 吕世光: "《塑料橡胶助剂手册》", 30 September 1995, 中国轻工业出版社 * |
| 吕常钦: "《丙烯酸及酯生产与管理》", 31 July 2009, 中国石化出版社 * |
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Application publication date: 20160817 |