CN102268182A - Polycarbonate-acrylonitrile butadiene styrene(ABS) flame-retarding composition and preparation method thereof - Google Patents
Polycarbonate-acrylonitrile butadiene styrene(ABS) flame-retarding composition and preparation method thereof Download PDFInfo
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- CN102268182A CN102268182A CN2011101457504A CN201110145750A CN102268182A CN 102268182 A CN102268182 A CN 102268182A CN 2011101457504 A CN2011101457504 A CN 2011101457504A CN 201110145750 A CN201110145750 A CN 201110145750A CN 102268182 A CN102268182 A CN 102268182A
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- polycarbonate
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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
-
- 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
- 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)
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Abstract
The invention discloses a polycarbonate-ABS flame-retarding composition and a preparation method thereof. The polycarbonate-ABS flame-retarding composition comprises the following components: A, 40 to 99 weight parts of aromatic polycarbonate and/or polyestercarbonate; B, 0.5 to 60 weight parts of rubber modified thermoplastic copolymer; C, 0 to 45 weight parts of thermoplastic vinyl copolymer; D, 0.5 to 20 weight parts of phosphorous oligomer; and E, 0 to 5 weight parts of fluorinated polyolefin. The sodium ion content in the component D is lower than 5ppm. Through research on the basis of the conventional polycarbonate-ABS composition, the Na residue in the component D can catalyze the degradation of a polycarbonate (PC) component in a PC/ABS material and therefore leads to the degradation of the whole material and consequently influences of the thermostability of the composition. As a result, the method reduces the Na content in the component D to 5ppm, so that the composite has high thermostability and has necessary mechanical performance and flame-retarding performance.
Description
Technical field
The present invention relates to a kind of fire-retardant polycarbonate-ABS composition of phosphorus compound of using, said composition has shown excellent flame-retardant and mechanical property, particularly at high temperature has good thermal stability.
Background technology
The PC/ABS alloy of polycarbonate or itself and ABS blend preparation is widely used in electronic apparatus, photoprinter, duplicating machine, printer, facsimile recorder, computer, notebook, portable computer, and other business automation equipments, portable phone and other communication equipment.In recent years, in these are used, many times require these product surfaces that very high gloss is arranged, this just requires material that low-down low molecular weight volatile thing must be arranged when injection moulding, could guarantee that high-gloss surface does not have open defect.When guaranteeing that material has excellent appearance, also require material to have good mechanical property, processing characteristics, flame retardant properties.
EP-A-5 061 745 has described by aromatic copolycarbonate, the moulding compound that graftomer and phosplate form.Use phosplate as fire retardant in the composition.The volatility meeting grievous injury processing characteristics of phosplate, and may disadvantageous effect be arranged to processing units.
CN1178987C has described by aromatic copolycarbonate, the moulding compound that the ABS graftomer of rubber content＜25% and low polyphosphate form.Be the stress cracking performance that obtains, the content of phosphoric acid ester should not surpass 8%.But so low flame retardant agent content may not provide enough flame retardant propertiess.
CN1153804 has described the polymkeric substance of organic phosphate flame-retardant, when using the graft copolymer that limits granularity, can obtain excellent mechanical property, can produce the low molecular weight volatile thing but can predict material in the course of processing, what be unfavorable for high yield obtains the high gloss appearance effect.
Described among the CN1174048C by aromatic copolycarbonate, the composition that abs polymer and low polyphosphate form, said composition has better physical performance and anti-hydrolytic performance.But its resistance toheat can further improve.
" thermostability " is meant that under comparatively high temps, material does not have obvious variation on physicals.Have preferably that thermostability is meant that at high temperature considerable change does not take place for the performance and the flowability of material, be meant material its physicals at high temperature, mobile considerable change can take place and have relatively poor thermostability.
Application number is 99813447.3, denomination of invention is the Chinese invention patent of " flame-resistant polycarbonate-ABS moulding material ", a kind of thermoplastic composition is disclosed, it is made up of A, B, C, D and five components of E, wherein the D component unavoidably is bound to contain impurity Na, does not consider in this patent of invention that Na content is to effect of material performance.
Summary of the invention
The objective of the invention is to overcome the deficiency that existing flame-resistant polycarbonate ABS heat stability of composition exists, a kind of flame-resistant polycarbonate ABS composition with superior heat-stability, mechanical property and flame retardant properties is provided.
To achieve these goals, the present invention adopts following technical scheme:
A kind of polycarbonate-ABS fire-retardant combination, composed of the following components:
A:40-99 weight part aromatic copolycarbonate and/or polyestercarbonate;
The thermoplastic copolymer of the modified rubber of B:0.5-60 weight part, rubber is dispersed in the thermoplastic copolymer with the form of disperse phase, and portion of hot plastic copolymer chemical graft is to rubber;
Thermoplastic ethylene's base co-polymer of C:0-45 weight part;
The oligomeric phosphorus compound of the general formula of D:0.5-20 weight part (I),
（Ⅰ）
R wherein
1, R
2, R
3, R
4Be aryl independent of each other or optional being replaced by alkyl and/or halogen; N representative 0 independent of each other or 1; N represents 0-30; The X representative contains list or a plurality of aromatic group of 6-30 carbon atom;
The fluoro polyolefine of E:0-5 weight part;
It is characterized in that: the sodium ions content in the described D component is lower than 5ppm.
In above-mentioned polycarbonate-ABS fire-retardant combination, the preferred weight umber of described each component is:
A：60-98.5
B：1-40
C：0-25
D：1-18
E：0.1-3。
In above-mentioned polycarbonate-ABS fire-retardant combination, the aromatic copolycarbonate of component A and/or polyestercarbonate are known in the document, perhaps can be prepared with the currently known methods in the document (for the preparation of aromatic copolycarbonate can referring to, as US4487896, US5411999 for the preparation of aromatic polyester carbonate can referring to, as US3169121; US4487896.The preparation of aromatic copolycarbonate be by, as diphenol and carboxylic acid halide, preferred phosgene and/or with the aromatic dicarboxylic acid dihalide, preferred phthalic acid dihalide, adopt interfacial polymerization method, optional use chain terminator such as single phenol and optional use three-functionality-degree or react as triphenol or four phenol more than the branching agent of three-functionality-degree and to carry out.The weight-average molecular weight of polycarbonate (Mw is by ultracentrifuge method or light scattering determining) is 10000-200000, preferred 20000-80000.The carbonic ether structural content of aromatic polyester carbonate can change as required.Preferred carbonate group mass contg accounts for maximum 100% mole of the ratio of total amount (ester group and carbonate group summation), preferred maximum 80% mole, more preferably maximum 50%.Aromatic polyester carbonate learns that group and carbonate group both can distribute with block or random fashion in multipolymer.Polyestercarbonate and polycarbonate can use separately, also can mix use as required.
In above-mentioned polycarbonate-ABS fire-retardant combination, in the B component, described rubber is by polyhutadiene or Polybutadiene-styrene multipolymer, and acrylic elastomer, silicon rubber or ethylene-propylene elastoprene are formed; Thermoplastic copolymer is selected from vinyl aromatic monomers by one or more and the vinyl unsaturated nitrile monomer is polymerized.Described thermoplastic copolymer is formed by vinylbenzene, vinyl toluene and acrylonitrile monemer copolymerization, or is formed by vinylbenzene and acrylonitrile monemer copolymerization, or is formed by vinyl toluene and acrylonitrile monemer copolymerization.
In above-mentioned polycarbonate-ABS fire-retardant combination, for B component, the thermoplastic resin rubber phase of the modified rubber that the present invention uses is dispersed in the successive thermoplastic matrix as disperse phase, and wherein portion of hot plastic substrate chemical graft is to rubber phase.This rubber modified thermoplastic resin gathers by body and makes, and concrete grammar can be referring to US2646418; US 3243481; US 4254236 and US 5414045.
The rubber that is used to prepare rubber phase is that second-order transition temperature (Tg) is less than or equal to 25 ℃, preferably is less than or equal to 0 ℃, more preferably less than or equal-30 ℃ polymkeric substance.Tg can be measured by the differential scanning calorimeter.20 ℃/min of rate of heating.Flex point when the Tg value promptly is DSC curve glass transition.In preferred testing program, this rubber is linear polymer, and this polymkeric substance comprises one or more conjugated diene monomeric units.For example, 1.3-divinyl or the like.
In above-mentioned polycarbonate-ABS fire-retardant combination, for component C, at least a vinyl aromatic compounds that is selected from of monomer of thermoplastic ethylene's base co-polymer of the present invention, vinyl nitrilation thing (unsaturated nitrile), (methyl) alkyl acrylate etc.The multipolymer of the vinyl aromatic compounds (as vinylbenzene, alpha-methyl styrene, p-methylstyrene etc.) of preferred especially 60-80 weight % and the vinyl nitrilation thing (vinyl cyanide, methacrylonitrile etc.) of 20-40 weight %.This multipolymer can be prepared by radical polymerization, and preferable weight-average molecular weight is 15000-200000.
In above-mentioned polycarbonate-ABS fire-retardant combination, as preferably, in the described D component, R1, R2, R3 and R4 are phenyl, and n is 1.
In above-mentioned polycarbonate-ABS fire-retardant combination, said composition comprises at least a from stablizer, impact modifying agent, pigment, releasing agent, the additive of flow improver additive and static inhibitor.
In above-mentioned polycarbonate-ABS fire-retardant combination, for component D,
（Ⅰ）
R wherein
1, R
2, R
3, R
4Be aryl independent of each other or optional being replaced by alkyl and/or halogen; N representative 0 independent of each other or 1; N represents 0-30; The X representative contains list or a plurality of aromatic group of 6-30 carbon atom; X is for being preferably following structure:
Owing to when synthetic component D, will wash with water, can contain Na in the water, so existing component D is certain to contain residual Na.The present invention finds the PC component degradation in the Na energy catalysis PC/ABS material, causes whole material property deterioration, and then has influence on the thermostability of composition.The present invention finds that composition has excellent thermostability, and has the mechanical property and the flame retardant properties of necessity when the Na content among the component D being dropped to when being lower than 5ppm.As for the Na content that reduces among the component D diversified method can be arranged, for example adopt the very high water of purity to wash and get final product.
In above-mentioned polycarbonate-ABS fire-retardant combination, for component E, fluorinated polyolefin has high molecular effectively to provide anti-drippage property to resin combination.The fluoropolymer that uses and being used to prepares the method for this fluoropolymer can be referring to US3671487, US3723373 and US3383092.Comparatively difficult owing to fluoropolymer directly being added among the thermoplastic resin composition, therefore preferably in some way this fluoropolymer and second kind of polymkeric substance are coated in advance.For example the aqueous dispersions of fluoropolymer by the mode of letex polymerization, can be coated one layer of polymeric on the fluoropolymer surface.Concrete grammar can be referring to EP0739914A1.The multipolymer of polymer covering layer optimization styrene and vinyl cyanide, styrene comprise 60-90% weight wherein, vinyl cyanide accounts for 10-40% weight.Best fluorinated polyolefin is tetrafluoroethylene or polyvinylidene difluoride (PVDF).
Preparation of compositions method of the present invention is not limited especially, and each component is mixed, and extrudes by single screw rod or twin screw extruder, and the temperature of extruding is 220-300 ℃.
Compared with prior art, the present invention has following beneficial effect: the present invention studies on the basis of existing polycarbonate-ABS composition, find the PC component degradation in the Na energy catalysis PC/ABS material residual among the component D, cause whole material property deterioration, and then have influence on the thermostability of composition.Therefore the present invention drops to the Na content among the component D and is lower than 5ppm, and at this time composition has excellent thermostability, and has necessary mechanical property and flame retardant properties.
Embodiment
Following embodiment will be described in further detail the present invention, but the present invention should not be subjected to the restriction of these embodiment.
Each embodiment is 400rpm by screw speed, and barrel zone temperature is that 230-250 ℃ twin screw extruder mixes, and extruded stock is cut into particle.
Adopt shake moral Easymaster injection moulding machine the particle for preparing to be injection molded into the batten that needs.Injecting condition comprises: 240 ℃ of barrel zone temperatures, 60 ℃ of die temperatures.
1) notched Izod impact strength is according to the ISO179 canonical measure
2) tensile strength and elongation at break be according to the ISO527 canonical measure, draw speed 50mmmin
3) heat-drawn wire adopts the ISO75 canonical measure, load 1.82MPa, thickness 4mm.
4) density is according to the ISO1183 canonical measure
5) flame retardant properties is tested according to UL746
6) melting index (MFI) is according to ISO 1133 standard testings.260 ℃ of probe temperatures, load 2.16kg.
7) thermostability evaluation method:
In temperature is under 260 ℃ of conditions, and material is kept certain hour in injection moulding machine, be injection molded into batten again after, by above method test performance.
The present invention is verified by following embodiment:
Component A:PC resin
Caliber 300-10, viscosity 0.45, LG Dow POLYCARBONATE LTD. produces
B component: ABS resin
The tall company of ABS 8391 states produces, and substance law is synthetic
Component C:AS multipolymer
AS350, the tall company of state produces, and substance law is synthetic
Component D:
Phosphate compound
D1, Zhejiang ten thousand fills limit company and produces, sodium ions content 0ppm
D2, Zhejiang ten thousand fills limit company and produces, sodium ions content 2ppm
D3: Zhejiang ten thousand fills limit company and produces, sodium ions content 5ppm
D4: Zhejiang ten thousand fills limit company and produces, sodium ions content 50ppm
Component E: anti-dripping agent
TN-3500, last Hai'an Joanna Trollope company produces, PTFE content 50%
Embodiment 1～6 has verified the effect the when phosphoric acid ester of different sodium ions contents is used for composition, and detailed data the results are shown in Table 1:
Table 1, embodiment formula table and composite properties detected result
Experimental result by above-mentioned example can find out significantly that each embodiment has flame retardant properties preferably.Along with the minimizing of sodium ions content in the D component, material is under high temperature (260 ℃), and the elongation at break conservation rate improves.At high temperature the hold-time long more, the melting index of material is high more.The raising of MFI can think that the degraded of material causes, and with the reduction of sodium ions content in the D component, the rangeability of MFI reduces.Promptly along with the reduction of sodium ions content in the D component, the thermostability of material improves.
Claims (7)
1. polycarbonate-ABS fire-retardant combination, composed of the following components:
A:40-99 weight part aromatic copolycarbonate and/or polyestercarbonate;
The thermoplastic copolymer of the modified rubber of B:0.5-60 weight part, rubber is dispersed in the thermoplastic copolymer with the form of disperse phase, and portion of hot plastic copolymer chemical graft is to rubber;
Thermoplastic ethylene's base co-polymer of C:0-45 weight part;
The oligomeric phosphorus compound of the general formula of D:0.5-20 weight part (I),
（Ⅰ）
R wherein
1, R
2, R
3, R
4Be aryl independent of each other or optional being replaced by alkyl and/or halogen; N representative 0 independent of each other or 1; N represents 0-30; The X representative contains list or a plurality of aromatic group of 6-30 carbon atom;
The fluoro polyolefine of E:0-5 weight part;
It is characterized in that: the sodium ions content in the described D component is lower than 5ppm.
2. polycarbonate-ABS fire-retardant combination according to claim 1 is characterized in that the parts by weight of described each component are:
A：60-98.5
B：1-40
C：0-25
D：1-18
E：0.1-3。
3. according to claim 1 or 2 described polycarbonate-ABS fire-retardant combinations, it is characterized in that described rubber is by polyhutadiene or Polybutadiene-styrene multipolymer, acrylic elastomer, silicon rubber or ethylene-propylene elastoprene are formed; Thermoplastic copolymer is selected from vinyl aromatic monomers by one or more and the vinyl unsaturated nitrile monomer is polymerized.
4. according to the described polycarbonate-ABS fire-retardant combination of claim 3, it is characterized in that, thermoplastic copolymer is formed by vinylbenzene, vinyl toluene and acrylonitrile monemer copolymerization, or is formed by vinylbenzene and acrylonitrile monemer copolymerization, or is formed by vinyl toluene and acrylonitrile monemer copolymerization.
5. according to claim 1 or 2 described polycarbonate-ABS fire-retardant combinations, it is characterized in that, in the described D component, R
1, R
2, R
3And R
4Be phenyl, n is 1.
6. according to claim 1 or 2 described polycarbonate-ABS fire-retardant combinations, it is characterized in that said composition comprises at least a from stablizer, impact modifying agent, pigment, releasing agent, the additive of flow improver additive and static inhibitor.
7. the preparation method of the described polycarbonate-ABS fire-retardant combination of claim 1 is characterized in that comprising the steps: each component is mixed, and extrudes by single screw rod or twin screw extruder, and the temperature of extruding is 220-300 ℃.
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|---|---|---|---|
| CN2011101457504A CN102268182A (en) | 2011-06-01 | 2011-06-01 | Polycarbonate-acrylonitrile butadiene styrene(ABS) flame-retarding composition and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102757633A (en) * | 2012-07-03 | 2012-10-31 | 金发科技股份有限公司 | PC (poly carbonate) composite material, as well as preparation method and applications thereof and plastic product |
| CN104962059A (en) * | 2015-06-18 | 2015-10-07 | 金发科技股份有限公司 | Polycarbonate composition and method for preparing same |
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|---|---|---|---|---|
| CN1218070A (en) * | 1997-09-04 | 1999-06-02 | 通用电气公司 | Impact modified carbonate polymer composition having improved resistance to degradation and improved thermal stability |
| CN1266449A (en) * | 1997-08-11 | 2000-09-13 | 拜尔公司 | Flame resistant ABS polycarbonate mouldable materials |
| CN1326488A (en) * | 1998-11-18 | 2001-12-12 | 拜尔公司 | Flame-resistant polycarbonate-ABS moulding material |
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2011
- 2011-06-01 CN CN2011101457504A patent/CN102268182A/en active Pending
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| CN1266449A (en) * | 1997-08-11 | 2000-09-13 | 拜尔公司 | Flame resistant ABS polycarbonate mouldable materials |
| CN1218070A (en) * | 1997-09-04 | 1999-06-02 | 通用电气公司 | Impact modified carbonate polymer composition having improved resistance to degradation and improved thermal stability |
| CN1326488A (en) * | 1998-11-18 | 2001-12-12 | 拜尔公司 | Flame-resistant polycarbonate-ABS moulding material |
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| 《精细石油化工进展》 20041231 钱伯章 日本开发从废PC中回收双酚A的工艺 第14页 1-7 第5卷, 第3期 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102757633A (en) * | 2012-07-03 | 2012-10-31 | 金发科技股份有限公司 | PC (poly carbonate) composite material, as well as preparation method and applications thereof and plastic product |
| CN104962059A (en) * | 2015-06-18 | 2015-10-07 | 金发科技股份有限公司 | Polycarbonate composition and method for preparing same |
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Application publication date: 20111207 |