CN102146202A - Flame-retardant PC (polycarbonate) /ABS (Acrylonitrile Butadiene StyreneAcrylonitrile Butadiene Styrene) alloy for screw hole cracking resistance experiment and preparation method thereof - Google Patents
Flame-retardant PC (polycarbonate) /ABS (Acrylonitrile Butadiene StyreneAcrylonitrile Butadiene Styrene) alloy for screw hole cracking resistance experiment and preparation method thereof Download PDFInfo
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- CN102146202A CN102146202A CN2011100995336A CN201110099533A CN102146202A CN 102146202 A CN102146202 A CN 102146202A CN 2011100995336 A CN2011100995336 A CN 2011100995336A CN 201110099533 A CN201110099533 A CN 201110099533A CN 102146202 A CN102146202 A CN 102146202A
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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
- B29C48/03—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
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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
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
-
- 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
- B29C48/78—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling
- B29C48/875—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling for achieving a non-uniform temperature distribution, e.g. using barrels having both cooling and heating zones
-
- 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
- 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
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a flame-retardant PC (polycarbonate) /ABS (Acrylonitrile Butadiene StyreneAcrylonitrile Butadiene Styrene) alloy for a screw hole cracking resistance experiment and a preparation method thereof. The PC/ABS alloy is prepared from the following raw materials in part by weight: 68 to 80 parts of PC, 6 to 12 parts of ABS, 5 to 10 parts of SAN (Styrene Acrylonitrile), 0 to 6 parts of styrene-imide-maleic anhydride-N-aminoethyl piperazidine quadripolymer and 9 to 15 parts of BDP (beclometasone dipropionate). The preparation method of the PC/ABS alloy comprises the following steps of: mixing the PC, the ABS, the SAN and anhydride-N-aminoethyl piperazidine quadripolymer in an intermediate speed mixer; charging the mixed raw materials into a double-screw extruder; laterally feeding the BDP into the double-screw extruder; carrying out melting extrusion; and granulating to obtain the PC/ABS alloy. In the invention, the screw hole cracking performance of a product subjected to injection molding is improved by adding the styrene-imide-maleic anhydride-N-aminoethyl piperazidine quadripolymer serving as a reactive compatibilizer.
Description
Technical field
The present invention relates to a kind of Alloy And Preparation Method of technical field of polymer materials, specifically, what relate to is the fire retardation PC/ABS Alloy And Preparation Method of a kind of anti-screw hole cracking experiment.
Background technology
PC is the amorphism engineering plastics, has good resistance to impact shock, thermally-stabilised, glossiness, inhibition bacterium characteristic, flame-retarding characteristic and resistance to crocking.But because of molecular rigidity and sterically hindered bigger, its melt temperature higher (270--320 ℃) processing difficulties be difficult to make the large thin-wall goods, and unrelieved stress is bigger in the goods, and stress cracking easily takes place.Simultaneously PC is to the breach sensitivity, though PC to acidity and oils media stabilize, not alkaline-resisting, these have limited PC and have been restricted in actual applications.And ABS resin has excellent machinability and mechanical property.Therefore PC/ABS is a kind of polyblend of processing characteristics excellence, and its performance and price are between PC and ABS, and it compares it, and to have melt viscosity low with PC, advantages such as processing characteristics excellence.
The Gao Gang of PC/ABS alloy, high-ductility, high working property and flame retardant resistance after adding phosphorus flame retardant plasticising, are fit to be applied to household appliances very much.Can carry out the screw assembly work when household appliances assemble mostly, therefore the anti-screw hole performance to material has higher requirement.
PC/ABS alloy material flexible patent has appearred in the prior art much improving, such as publication number is the Chinese invention patent of CN101418118A, this invention provides that " a kind of halogen-free flame retardant PC/ABS Alloy And Preparation Method, its component and weight proportion are: PC 70-90 part, ABS 5-25 part, compatilizer 3-7 part, toughner 3-8 part, fire retardant phosphoric acid ester organism 9-16 part, PTFE 0.3-1.5 part, silicone resin 2-8 part, nanometer inorganic filler 0.4-1.5 part, oxidation inhibitor 0.1-0.5 part." and for example; publication number is the Chinese invention patent of CN101003671A; this invention " relates to the prescription that a kind of PC reclaimed materials is modified as high tenacity fire retardation PC/ABS alloy, form by the following component of calculating according to the mass fraction: PC reclaimed materials: 45～60 parts, ABS:20～35 part, grafts: 1～5 part, acrylic acid esters co-polymer: 3～10 parts, Resins, epoxy: 0.1～1 part, oxidation inhibitor: 0.1～0.5 part, bromide fire retardant: 6～12 parts, Sb system fire retardant: 1～2 part, inorganic combustion inhibitor: 1～2 part, 0.2～0.8 part of tetrafluoroethylene.”
The screw hole results of property can explain that cracking generally appears at the poorest position of toughness of material with Law of Barrel, by defective rubber phase decision.Be directed to this, the invention provides the fire retardation PC/ABS Alloy And Preparation Method of a kind of anti-screw hole cracking experiment.
Summary of the invention
The objective of the invention is to solve above-mentioned deficiency of the prior art, fire retardation PC/ABS the Alloy And Preparation Method of a kind of anti-screw hole cracking experiment is provided, by adding the quarternary copolymerized response type compatilizer of vinylbenzene-imide-maleic anhydride-N-aminoethyl piperazine, improve the cracking performance of the screw hole of the product after the injection moulding.
For achieving the above object, the invention provides the fire retardation PC/ABS alloy of a kind of anti-screw hole cracking experiment, form by the starting material configuration of following weight parts proportioning:
PC 68-80 part;
ABS 6-12 part;
SAN 5-10 part;
Vinylbenzene-imide-maleic anhydride-N-aminoethyl piperazine tetrapolymer 0-6 part;
BDP 9-15 part.
Described polycarbonate weight-average molecular weight is 20000-30000, optimization aromatic, especially preferred bisphenol A polycarbonate.
Described ABS weight-average molecular weight is 80000-150000, and wherein rubber content is 40-60%, and acrylonitrile content is 10-15%, and styrene content is 25-50%.Described content is weight percentage.
Described SAN weight-average molecular weight is 100000-150000, and its vinyl cyanide weight percentage is 24-32%.
Described vinylbenzene-imide-maleic anhydride-N-aminoethyl piperazine tetrapolymer, its structural formula is as follows:
Described BDP is that dihydroxyphenyl propane-two (diphenyl phosphoesters) are fire retardant, and its structural formula is as follows:
The present invention also provides the preparation method of the fire retardation PC/ABS alloy of above-mentioned anti-screw hole cracking experiment, may further comprise the steps:
A. take by weighing described raw material according to weight ratio;
B. PC, ABS, SAN and compatilizer are mixed 20min in moderate-speed mixers;
C. throw into above-mentioned mixed raw material in twin screw extruder, the BDP side feeds, through melt extruding granulation.
Described twin screw extruder comprises ten temperature controlled region, the temperature in described temperature control 1-2 district is 200-260 ℃, and the temperature in temperature control 3-4 district is 200-260 ℃, and the temperature in temperature control 5-6 district is 200-260 ℃, the temperature in temperature control 7-8 district is 200-260 ℃, and the temperature in temperature control 9-10 district is 200-260 ℃; Described twin screw extruder has two to vacuumize the place, and wherein a place is positioned at the end of material conveying section, the starting end of melt zone; Another place's vaccum-pumping equipment is positioned at metering zone.
At present, fire retardation PC/ABS material is widely applied to household appliances, and household appliances can carry out the screw assembly work when assembling mostly, and therefore the anti-screw hole performance to material has higher requirement.The present invention is by adding the quarternary copolymerized response type compatilizer of vinylbenzene-imide-maleic anhydride-N-aminoethyl piperazine, both can carry out graft reaction with PC, there is same functional group that thereby good consistency is arranged with ABS again, finally make the littler, more even of ABS dispersed phase distribution, the cracking performance of the screw hole of the product after the injection moulding that is improved.
Embodiment
The technical solution of the present invention is further explained below in conjunction with embodiment, but following content is not intended to limit the scope of the invention.
In following examples of the present invention, the raw material of employing is:
Selected PC is PC-300-15, and LG-Pow produces.
ABS is the ABS P/D150 with Korea Gumho Petrochemical Co., Ltd., ABS P/D190 or ABS P/D130, preferred ABS P/D150 among the embodiment.
SAN is the SAN320 with Korea Gumho Petrochemical Co., Ltd., and AN content is 24%.
Vinylbenzene-imide-maleic anhydride-N-aminoethyl piperazine tetrapolymer, Shanghai Kumbosunny Plastics CO.,LTD is synthetic, and synthetic method is to use the heat-resistant agent MSNI of NEC chemistry and the common extrusion reaction of N-aminoethyl piperazine to form.
That BDP adopts is the FP-700 in Changchun, Taiwan.
The preparation method who adopts in the embodiment of the invention is:
A. take by weighing described raw material according to weight ratio;
B. PC, ABS, SAN and compatilizer are mixed 20min in moderate-speed mixers;
C. throw into above-mentioned mixed raw material in twin screw extruder, the BDP side feeds, through melt extruding granulation.Wherein twin screw extruder comprises ten temperature controlled region, the temperature in described temperature control 1-2 district is 200-260 ℃, and the temperature in temperature control 3-4 district is 200-260 ℃, and the temperature in temperature control 5-6 district is 200-260 ℃, the temperature in temperature control 7-8 district is 200-260 ℃, and the temperature in temperature control 9-10 district is 200-260 ℃; Described twin screw extruder has two to vacuumize the place, and wherein a place is positioned at the end of material conveying section, the starting end of melt zone; Another place's vaccum-pumping equipment is positioned at metering zone.
As shown in table 1 below, totally 5 prescriptions then according to the ASTM standard, are injection molded into batten by above-mentioned mode of production granulation under same injecting condition, and test result is as follows:
Table 1
Remarks: fracture productivity test condition is 50mm/min; The screw hole experiment is to use the M4 screw, the torsion of 4KG, and 3 assembling screws see whether screw hole ftractures repeatedly, 10 screw holes are added up intact number.
From experimental result as can be seen, in fire retardation PC/ABS system, after having added vinylbenzene-imide-maleic anhydride-N-aminoethyl piperazine tetrapolymer, the elongation at break of material increases substantially, shock strength has improvement slightly but is not obvious, the cracking performance of anti-the screw hole promotes significantly, and the practical set of household appliances is had positive meaning.
Below only be the detailed description that preferred embodiment of the present invention is carried out, but the present invention is not limited to above embodiment.It should be understood that under the spirit and scope situation of the claim that does not break away from the application, the various modifications that those skilled in the art makes still belong to scope of the present invention.
Claims (10)
1. fire retardation PC/ABS the alloy of anti-screw hole cracking experiment is characterized in that being formed by the starting material configuration of following weight parts proportioning:
PC 68-80 part;
ABS 6-12 part;
SAN 5-10 part;
Vinylbenzene-imide-maleic anhydride-N-aminoethyl piperazine tetrapolymer 0-6 part;
BDP 9-15 part.
2. fire retardation PC/ABS the alloy of anti-screw hole cracking according to claim 1 experiment, it is characterized in that: described polycarbonate weight-average molecular weight is 20000-30000.
3. fire retardation PC/ABS the alloy of anti-screw hole cracking according to claim 1 and 2 experiment, it is characterized in that: described polycarbonate is an aromatic series.
4. fire retardation PC/ABS the alloy of anti-screw hole cracking according to claim 3 experiment, it is characterized in that: described polycarbonate is a bisphenol A polycarbonate.
5. fire retardation PC/ABS the alloy of anti-screw hole cracking according to claim 1 experiment, it is characterized in that: described ABS weight-average molecular weight is 80000-150000, wherein rubber content is 40-60%, acrylonitrile content is 10-15%, styrene content is 25-50%, and described content is weight percentage.
6. fire retardation PC/ABS the alloy of anti-screw hole cracking according to claim 1 experiment, it is characterized in that: described SAN weight-average molecular weight is 100000-150000, its vinyl cyanide weight percentage is 24-32%.
7. fire retardation PC/ABS the alloy of anti-screw hole cracking according to claim 1 experiment is characterized in that: described vinylbenzene-imide-maleic anhydride-N-aminoethyl piperazine tetrapolymer, and structural formula is as follows:
8. fire retardation PC/ABS the alloy of anti-screw hole cracking according to claim 1 experiment is characterized in that: described BDP, be dihydroxyphenyl propane-two (diphenyl phosphoesters), and structural formula is as follows:
9. the preparation method of the fire retardation PC/ABS alloy of an anti-screw hole cracking as claimed in claim 1 experiment is characterized in that: may further comprise the steps:
A. take by weighing described raw material according to weight ratio;
B. PC, ABS, SAN and vinylbenzene-imide-maleic anhydride-N-aminoethyl piperazine tetrapolymer is mixed 20min in moderate-speed mixers;
C. throw into above-mentioned mixed raw material in twin screw extruder, the BDP side feeds, through melt extruding granulation.
10. the preparation method of the fire retardation PC/ABS alloy of anti-screw hole cracking according to claim 9 experiment, it is characterized in that: described twin screw extruder comprises ten temperature controlled region, the temperature in described temperature control 1-2 district is 200-260 ℃, the temperature in temperature control 3-4 district is 200-260 ℃, the temperature in temperature control 5-6 district is 200-260 ℃, the temperature in temperature control 7-8 district is 200-260 ℃, and the temperature in temperature control 9-10 district is 200-260 ℃; Described twin screw extruder has two to vacuumize the place, and wherein a place is positioned at the end of material conveying section, the starting end of melt zone, and another place's vaccum-pumping equipment is positioned at metering zone.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100995336A CN102146202A (en) | 2011-04-20 | 2011-04-20 | Flame-retardant PC (polycarbonate) /ABS (Acrylonitrile Butadiene StyreneAcrylonitrile Butadiene Styrene) alloy for screw hole cracking resistance experiment and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN2011100995336A CN102146202A (en) | 2011-04-20 | 2011-04-20 | Flame-retardant PC (polycarbonate) /ABS (Acrylonitrile Butadiene StyreneAcrylonitrile Butadiene Styrene) alloy for screw hole cracking resistance experiment and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107163533A (en) * | 2017-05-26 | 2017-09-15 | 上海长伟锦磁工程塑料有限公司 | A kind of PC/ABS alloys of anti-screw hole cracking |
| CN111849114A (en) * | 2019-04-28 | 2020-10-30 | 合肥杰事杰新材料股份有限公司 | Modified regenerated composite plastic and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH083397A (en) * | 1994-06-24 | 1996-01-09 | Nippon G Ii Plast Kk | Flame retardant thermoplastic resin composition |
| CN101974216A (en) * | 2010-10-29 | 2011-02-16 | 大河宝利材料科技(苏州)有限公司 | Halogen-free flame-retardant PC/ABS alloy |
| CN101985516A (en) * | 2010-08-25 | 2011-03-16 | 上海锦湖日丽塑料有限公司 | Composite material for home appliance shell and preparation method thereof |
-
2011
- 2011-04-20 CN CN2011100995336A patent/CN102146202A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH083397A (en) * | 1994-06-24 | 1996-01-09 | Nippon G Ii Plast Kk | Flame retardant thermoplastic resin composition |
| CN101985516A (en) * | 2010-08-25 | 2011-03-16 | 上海锦湖日丽塑料有限公司 | Composite material for home appliance shell and preparation method thereof |
| CN101974216A (en) * | 2010-10-29 | 2011-02-16 | 大河宝利材料科技(苏州)有限公司 | Halogen-free flame-retardant PC/ABS alloy |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107163533A (en) * | 2017-05-26 | 2017-09-15 | 上海长伟锦磁工程塑料有限公司 | A kind of PC/ABS alloys of anti-screw hole cracking |
| CN111849114A (en) * | 2019-04-28 | 2020-10-30 | 合肥杰事杰新材料股份有限公司 | Modified regenerated composite plastic and preparation method thereof |
| CN111849114B (en) * | 2019-04-28 | 2022-04-26 | 合肥杰事杰新材料股份有限公司 | Modified regenerated composite plastic and preparation method thereof |
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Application publication date: 20110810 |