CN102643506B - Flame retardant permanent anti-static acrylonitrile butadiene styrene (ABS) /polyethylene terephthalate (PET) alloy and preparation method thereof - Google Patents

Flame retardant permanent anti-static acrylonitrile butadiene styrene (ABS) /polyethylene terephthalate (PET) alloy and preparation method thereof Download PDF

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Publication number
CN102643506B
CN102643506B CN201210135211.7A CN201210135211A CN102643506B CN 102643506 B CN102643506 B CN 102643506B CN 201210135211 A CN201210135211 A CN 201210135211A CN 102643506 B CN102643506 B CN 102643506B
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pet
abs
retardant
flame
pet alloy
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CN102643506A (en
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胡浩
姜苏俊
刘奇祥
宁方林
易庆锋
龙杰明
张超
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Kingfa Science and Technology Co Ltd
Shanghai Kingfa Science and Technology Co Ltd
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Kingfa Science and Technology Co Ltd
Shanghai Kingfa Science and Technology Co Ltd
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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
    • B29C48/50—Details of extruders
    • B29C48/505—Screws
    • B29C48/625—Screws characterised by the ratio of the threaded length of the screw to its outside diameter [L/D ratio]
    • 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
    • B29C48/92—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
    • B29C2948/9258—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
    • 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
    • B29C2948/92885—Screw or gear

Abstract

The invention discloses a flame retardant permanent anti-static acrylonitrile butadiene styrene (ABS) /polyethylene terephthalate (PET) alloy and a preparation method thereof. The flame retardant permanent anti-static ABS/ PET alloy includes the following components of, by weight, 45% to 72% of ABS resins, 2% to 10% of PET, 10% to 20% of permanent anti-static agents and 15% to 25% of flame retardants. The preparation method includes adding each of the components according to the ratio into a high speed mixer for evenly mixing, feeding the mixtures into a double-screw extruder, and subjecting the mixtures to mixing, extruding, drawing, cooling and granule-cutting, and obtaining the flame retardant permanent anti-static ABS/ PET alloy. The flame retardant permanent anti-static ABS/ PET alloy has a good tenacity, an excellent flame retardant performance and an excellent anti-static performance, and is capable of greatly reducing product costs on the premise of meeting basic applications.

Description

A kind of flame-retardant permanent antistatic ABS/PET Alloy And Preparation Method
Technical field
The invention belongs to functional high molecule material technical field, be specifically related to a kind of flame-retardant permanent antistatic ABS/PET Alloy And Preparation Method.
Background technology
ABS resin has excellent over-all properties, is widely used in household electrical appliance, electronic apparatus, and office equipment, automotive industry etc., is one of five large general-purpose plastics.But the oxygen index of ABS (OI) is 18, belongs to inflammable material, while being therefore applied to electrical equipment relevant industries, must carry out flame-retardant modified; And due to the unavoidable static that produces in the process of these electric equipment products of production, form static voltage, can cause electrostatic breakdown product, more serious meeting brings personal injury, and therefore, it is necessary that ABS material is eliminated to static.PET is also widely used a kind of material, and relative ABS is cheap for price, and easily reclaims.The recovery of PET has at present formed comparatively complete industrial system, and from the angle of economy and environmental protection, developing a flame-retardant permanent antistatic ABS/PET alloy is to adapt to socioeconomic development trend completely.
Chinese patent literature CN 101709126 A disclose in ABS resin by bromide fire retardant and the composite flame retardant effect that reaches of Sb system fire retardant, by adding the static inhibitor of small molecules type to reach antistatic effect, but the static inhibitor of small molecules type is easily along with the prolongation antistatic effect of time progressively disappears, and antistatic effect is very large to the dependency of ambient moisture, affected the practical application of material.
Chinese patent literature CN 102020825A discloses in ABS resin by Sb system fire retardant and the composite flame retardant effect that reaches of chlorinatedpolyethylene fire retardant, by adding a family macromolecule static inhibitor of polyethers fat or polyetheramides class to reach antistatic effect; By adding compatilizer to improve the consistency of ABS/PET; Chinese patent literature CN101857712A discloses the preparation method of a kind of halogen-free flame retardant ABS/PET, by the consistency that improves ABS/PET that adds of expanding material and toughner, by phosphorus flame retardant and the composite flame retardant effect that reaches of nitrogenated flame retardant.Although above-mentioned modified measures has improved the mechanical property of ABS/PET co-mixing system, because the expanding material and the toughner that use are expensive, thereby greatly increased the cost of material, greatly limited its application in industry.
Summary of the invention
In order to overcome the shortcoming and deficiency of prior art, primary and foremost purpose of the present invention is to provide a kind of flame-retardant permanent antistatic ABS/PET alloy, and this alloy has good toughness, possesses excellent flame retardant properties and antistatic property simultaneously.
Another object of the present invention is to provide the preparation method of above-mentioned flame-retardant permanent antistatic ABS/PET alloy.
The present invention is achieved by the following technical solutions:
A flame-retardant permanent antistatic ABS/PET alloy, by weight percentage, comprises following component:
ABS resin 45-72wt%
Regenerative PET 2-10wt%
Permanent anti-static agent 10-20wt%
Fire retardant 15-25wt%.
Regenerative PET of the present invention is that the broken granulation of PET bottle generates, and its limiting viscosity is 0.5-0.8dl/g, and this limiting viscosity adopts Ubbelohde viscometer according to GBT14190-2008 standard test.The present invention is controlled at 2-10wt% by the content of regenerative PET, and the ABS/PET alloy generating has good toughness, if the content of PET is greater than 10wt%, the toughness of alloy can sharply decline.
Described ABS resin is at 23 ℃, and the testing standard socle girder notched Izod impact strength according to ASTM D256 under 50% humidity condition is greater than 400J/M.
Permanent anti-static agent of the present invention is the permanent anionic antistatic agent of polyetheramides class, and in its molecular structure, hard section be that nylon, soft section are pfpe molecule chain, and its durometer level is 70A-95A, and surface resistivity is 10 6-10 9w.The permanent anti-static agent that the present invention selects must just have antistatic effect higher than 10wt%, and surface resistivity reaches 10 conventionally 12w, and permanent anti-static agent higher than 20wt% after the increase of antistatic effect not obvious, surface resistivity maintains 10 conventionally 8-10 9w, so the present invention is controlled at the content range of permanent anti-static agent between 10-20wt%, so that the alloy generating has excellent permanent antistatic performance.
Described fire retardant is the mixture of bromide fire retardant and stibium trioxide fire retardant, and wherein the weight ratio of bromide fire retardant and stibium trioxide fire retardant is between 3:1-4:1.
Described bromide fire retardant is three (tribromo phenyl) triazine, TDE or decabromodiphynly oxide preferably.
The present invention also comprises other additives, and described other additive is one or more the mixture in oxidation inhibitor, Yi support stearic bicine diester An ﹑ stearate.
Described oxidation inhibitor is any one or a few the mixture in oxidation inhibitor 1010 ﹑ oxidation inhibitor 168 ﹑ antioxidant 1076s.
The preparation method of flame-retardant permanent antistatic ABS/PET alloy of the present invention, comprises the steps:
A, by above-mentioned weight percentage, take each material;
B, add high-speed mixer to mix above-mentioned each material weighing up, the material that obtains mixing;
C, by the above-mentioned material mixing in precision meter feeding twin screw extruder, through overmulling refining ﹑, squeeze out ﹑ and draw the cold but ﹑ of bar ﹑ pelletizing to obtain flame-retardant permanent antistatic ABS/PET alloy.
In preparation method of the present invention, because PET easily absorbs water, when granulation, be very easily hydrolyzed, therefore PET is dried 3-4h at 100-120 ℃ before mixing, the rotating speed of high-speed mixer is arranged on 800-1200rpm, the length-to-diameter ratio of twin screw extruder is 35-45, and barrel temperature is controlled at 200-230 ℃, and screw speed is at 300-500 rev/min.
Compared with prior art, tool has the following advantages in the present invention:
1) the present invention has avoided the use of expensive expanding material and toughner in flame-retardant permanent antistatic ABS/PET alloy system, by the be hit by a bullet use of gonosome of permanent anti-static agent, reaches toughening effect; Simultaneously by the control of PET content and viscosity is reached to compatibilization effect; Under satisfied basic application prerequisite, significantly reduce product cost; Prepared flame-retardant permanent antistatic ABS/PET alloy has good toughness, and possesses excellent flame retardant properties and permanent antistatic property simultaneously.
In the present invention, can not only significantly reduce material cost adding of regenerative PET, is more conducive to the recycle after PET plastics are discarded.
Embodiment
Below by embodiment, further illustrate the present invention, following examples are preferably embodiment of the present invention, but embodiments of the present invention are not subject to the restriction of following embodiment.
Each component adopting in the embodiment of the present invention is as follows:
The ABS D-120A that ABS resin provides for Taiwan company.
PETWei company purchases voluntarily the broken granulation of PET bottle chips and forms, and its limiting viscosity is at 0.6 dl/g.
The bromide fire retardant FR-245 that fire retardant provides for Israel Dead Sea bromine company, the antimonous oxide that stibium trioxide Wei Huachangti industry company provides.
Permanent anti-static agent changes into the Pelestat 6500 that Industrial Co., Ltd provides for SANYO GS.
Oxidation inhibitor is that the antioxidant 1010 produced of Shanghai vapour bar (CIBA) elite company and irgasfos 168 are by weight the composite mixture forming of 1:2.
The HDC-102 that common static inhibitor provides for Linan, Hangzhou Dechang Chemical Co., Ltd. and HDC-201 are by weight the composite mixture forming of 2:1.
Other additives are domestic N, N-ethylene bis stearic acid amide (EBS).
First each component is pressed to proportioning, concrete recipe ratio, in Table 1, adds high-speed mixer to mix, and wherein PET is dried 4h at 120 ℃ before mixing, and the rotating speed of high-speed mixer is arranged on 1000rpm; Then said mixture is fed in twin screw extruder through precision meter, through overmulling refining ﹑, squeeze out ﹑ and draw the cold but ﹑ of bar ﹑ pelletizing; Wherein: the length-to-diameter ratio of twin screw extruder is 40:1, leading portion barrel temperature is controlled at 200-210 ℃, and stage casing temperature is controlled at 210-220 ℃, and head temperature is controlled at 220-230 ℃, and screw speed is at 400 revs/min.
Formula in each embodiment of table 1 and comparative example forms
Form (wt%) Embodiment 1 Embodiment 2 Embodiment 3 Comparative example 1 Comparative example 2
ABS D-120A 45 60 72 35 69
PET 10 5 2 25 5
FR-245 19.2 15.2 11.8 16 15.2
Stibium trioxide 5 4 3.4 4.2 4
Permanent anti-static agent 20 15 10 19 0
Antioxidant 1010 0.1 0.1 0.1 0.1 0.1
Irgasfos 168 0.2 0.2 0.2 0.2 0.2
EBS 0.5 0.5 0.5 0.5 0.5
Common static inhibitor 0 0 0 0 6
Above-described embodiment and the prepared flame-retardant permanent antistatic ABS/PET alloy of comparative example are injection molded into the test bars of standard, then according to the testing standard shown in table 2, carry out the performance test of sample, test result is in Table 3
Table 2 quantitative measurement standard
Performance index Test condition Testing method
Tensile strength 50mm/min ASTM D638
Elongation at break 50mm/min ASTM D638
Socle girder notched Izod impact strength 3.2mm, 23℃ ASTM D256
Flexural strength 2mm/min ASTM D790
Modulus in flexure 2mm/min ASTM D790
Surface resistivity The square plate (100*100mm) that 3.0m is thick IEC 61340-5-1
Flame retardant properties 3.0mm UL94
The performance test data of each embodiment of table 3
Performance index Embodiment 1 Embodiment 2 Embodiment 3 Comparative example 1 Comparative example 2
Tensile strength (MPa) 34.3 31.9 28.5 33.6 26.9
Elongation at break (%) 35 30 20 6 4
Socle girder notched Izod impact strength (J/M) 132 155 165 45 37
Flexural strength (MPa) 53 50 46 43.3 50
Modulus in flexure (MPa) 1737 1650 1550 1466 1692
Surface resistivity (W) 10 9 10 10 10 12 10 9 10 11
Flame retardant properties V-0 V-0 V-1 V-0 V-1
The performance test results from above-described embodiment and comparative example: prepared flame-retardant permanent antistatic ABS/PET alloy has good toughness, possesses excellent flame retardant properties and antistatic property simultaneously.

Claims (10)

1. a flame-retardant permanent antistatic ABS/PET alloy, is characterized in that, by weight percentage, comprises following component:
ABS resin 45-72wt%
PET 2-10wt%
Permanent anti-static agent 10-20wt%
Fire retardant 15-25wt%
Described permanent anti-static agent is for containing the permanent anionic antistatic agent of polyetheramides class.
2. flame-retardant permanent antistatic ABS/PET alloy according to claim 1, is characterized in that, described PET is that the broken granulation of PET bottle generates, and its limiting viscosity is 0.5-0.9dl/g.
3. flame-retardant permanent antistatic ABS/PET alloy according to claim 1, is characterized in that, described ABS resin is at 23 ℃, and the testing standard socle girder notched Izod impact strength according to ASTM D256 under 50% humidity condition is greater than 400J/M.
4. flame-retardant permanent antistatic ABS/PET alloy according to claim 1, is characterized in that, described fire retardant is the mixture of bromide fire retardant and stibium trioxide fire retardant, and the weight ratio of bromide fire retardant and stibium trioxide fire retardant is between 3:1-4:1.
5. flame-retardant permanent antistatic ABS/PET alloy according to claim 4, is characterized in that, described bromide fire retardant is three (tribromo phenyl) triazine, TDE or decabromodiphynly oxide.
6. flame-retardant permanent antistatic ABS/PET alloy according to claim 1, is characterized in that, also comprises other additive, and other additives are one or more the mixture in oxidation inhibitor, Yi support stearic bicine diester An ﹑ stearate.
7. flame-retardant permanent antistatic ABS/PET alloy according to claim 6, is characterized in that, described oxidation inhibitor is any one or a few the mixture in oxidation inhibitor 1010 ﹑ oxidation inhibitor 168 ﹑ antioxidant 1076s.
8. the preparation method of the flame-retardant permanent antistatic ABS/PET alloy described in claim 1 ~ 7 any one, is characterized in that, comprises the steps:
A, by weight percentage claimed in claim 1, take each material;
B, add high-speed mixer to mix above-mentioned each material weighing up, the material that obtains mixing;
C, by the above-mentioned material mixing in precision meter feeding twin screw extruder, through overmulling refining ﹑, squeeze out ﹑ and draw the cold but ﹑ of bar ﹑ pelletizing to obtain flame-retardant permanent antistatic ABS/PET alloy.
9. the preparation method of flame-retardant permanent antistatic ABS/PET alloy according to claim 8, is characterized in that the rotating speed of described high-speed mixer is arranged on 800-1200rpm.
10. the preparation method of flame-retardant permanent antistatic ABS/PET alloy according to claim 8, the length-to-diameter ratio that it is characterized in that described twin screw extruder is 35-45, and barrel temperature is controlled at 200-230 ℃, and screw speed is at 300-500 rev/min.
CN201210135211.7A 2012-05-04 2012-05-04 Flame retardant permanent anti-static acrylonitrile butadiene styrene (ABS) /polyethylene terephthalate (PET) alloy and preparation method thereof Active CN102643506B (en)

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CN101265404A (en) * 2007-03-12 2008-09-17 深圳市科净科技有限公司 Permanent antistatic copolymer material and processing method thereof
CN101497733A (en) * 2008-02-03 2009-08-05 绵阳长鑫新材料发展有限公司 High-performance low-cost flame-retardant ABS/PET alloy material
CN101418111B (en) * 2008-11-14 2013-03-20 上海金发科技发展有限公司 Weather resistant flame retardant ABS resin and preparation process thereof
CN101508818A (en) * 2008-12-17 2009-08-19 深圳市科聚新材料有限公司 ABS//PET alloy and method for producing the same
CN101870797B (en) * 2010-03-29 2013-07-03 金发科技股份有限公司 Polyacrylonitrile-butadiene-styrene modified compound and preparation method thereof

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