CN104004313A - ABS resin composition for electroplating and preparation method thereof - Google Patents
ABS resin composition for electroplating and preparation method thereof Download PDFInfo
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- CN104004313A CN104004313A CN201410186859.6A CN201410186859A CN104004313A CN 104004313 A CN104004313 A CN 104004313A CN 201410186859 A CN201410186859 A CN 201410186859A CN 104004313 A CN104004313 A CN 104004313A
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Abstract
The invention discloses ABS resin composition for electroplating and a preparation method thereof. The electroplating ABS resin composition with excellent heat stability and electroplating practicability is prepared by controlling the grafting ratio of grafted ABS polymer, the total amount of oligomers and residual monomers in SAN copolymer and the vacuum degree during extrusion mixing, and the molding yield of electroplated products and the electroplating yield are substantially improved.
Description
Technical field
The invention belongs to technical field of macromolecules, especially relate to a kind of electroplating ABS resin combination and preparation method thereof.
Background technology
Plastic electroplating part is widely used on the inside and outside ornamental part of automobile, such as vehicle label, sign, anti-friction panel, radiator grid, wheel cover, inside door handle, gear panel etc.Plated item on market more than 90% is that blend taking ABS or ABS is as plating substrate.Along with being growing more intense of market competition, require improve the moulding yield of plastics blank and electroplate yield, therefore, thermostability and electrodepositable to ABS material have proposed requirements at the higher level.If the thermostability of ABS is not good, when injection moulding, the amount of being fuming and smell are large, and injection moulding blank surface there will be filamentary silver, gas trace, white mist, xanthochromia etc. obviously bad; If the electrodepositable of ABS is not good, ABS goods are easy to occur plating leakage defect.Graft ratio in the thermostability of ABS and electrodepositable and grafted ABS polymkeric substance is closely related.Graft ratio is defined as the ratio of the weight of grafted monomer and the weight of rubber.Graft ratio is low, and the exposed rubber latex content of grafting is not high, poor heat stability; Graft ratio is low, and the dispersion of grafted ABS polymkeric substance in san copolymer is also poor.Graft ratio is high, and between molecule, strong Van der Waals force makes the dispersion of grafted ABS polymkeric substance in SAN also bad, electroplates accordingly ABS and easily occurs plating leakage.
In prior art report, be the thermostability that improves ABS resin by adding the stable on heating method of the 4th component raising ABS resin mostly.Such as the publication number patent of invention that is CN1383444A, disclose a kind of prepare ABS resin with superior heat-stability by the method for mixed grafting abs polymer and heat-resistant copolymer method, heat-resistant copolymer is preferably alpha-methyl styrene-acrylonitritrile-styrene resin.The introducing of heat-resistant agent has increased material cost, has also sacrificed the processibility of ABS, has reduced the mobility of material, has increased the moulding internal stress of goods.Publication number is that the patent of CN102653582A discloses and a kind ofly prepares the method for electroplating ABS resin, the synthesis technique more complicated of grafted ABS polymkeric substance and wayward by rubber morphological structure, rubber size and the grafting thickness controlled in grafted ABS polymkeric substance.
Summary of the invention
The present invention is in order to overcome above-mentioned deficiency, and the preparation method of the electroplating ABS resin combination that a kind of thermostability and electrodepositable performance be improved is simultaneously provided.
Technical scheme of the present invention is as follows, the present invention relates to a kind of electroplating ABS resin combination, comprise that weight percentage is the san copolymer that 20～50% grafted ABS polymkeric substance and weight percentage are 50～80%, the graft ratio of described grafted ABS polymkeric substance is 45%～75%, and in san copolymer, the residual list of styrene monomer and acrylonitrile monemer composition and oligopolymer total amount are lower than 5000ppm.
The weight percentage of the divinyl in described grafted ABS polymkeric substance is 40～70%, and the median size of divinyl is 200～350nm, and divinyl rubber degree of crosslinking is 75～95%; The weight percentage of vinyl cyanide is 5～20%; Cinnamic weight percentage is 15～40%.
The relative molecular mass of described san copolymer is 40000～400000g/mol, and the weight percentage of vinyl cyanide is 15～35%.
Above-mentioned electroplating ABS resin combination adopts following methods to make:
(1) prepare respectively the step of grafted ABS polymkeric substance and san copolymer;
(2) step of the grafted ABS polymkeric substance, san copolymer and the heat-resistant agent that prepare and auxiliary agent being mixed to 30min in proportion in high-speed mixer;
(3) above-mentioned mixed mixture is entered from the main feeding of twin screw extruder, through the step melt extruding, cooling, dry, pelletizing obtains sample.
The described middle grafted ABS polymkeric substance of step (1) is under divinyl rubber emulsion exists, and mixes tertiary lauryl mercaptan and benzoyl peroxide carries out graft polymerization with styrene monomer, acrylonitrile monemer, then makes after condensing, dewater, being dried; Described san copolymer by the styrene monomer mixing Diisopropyl azodicarboxylate of the acrylonitrile monemer of 15～35 weight parts, 65～85 weight parts, tert-dodecyl mercaptan via mass polymerization and remove volatile component and make.Wherein, divinyl rubber emulsion is to be aggregated in advance after the small particle size rubber latex of 0.07～0.15 μ m by divinylic monomer, then with the method for pressure agglomeration, the small particle size rubber hypertrophy of 0.07～0.15 μ m is become to the rubber latex of 0.2～0.35 μ m.
In step (2), grafted ABS polymkeric substance and san copolymer are pressed 1:4～1:1 mixing.
In step (3), twin screw extruder is prepared the resin of particle form under 210～230 DEG C of processing temperatures, and in the machine barrel of twin screw extruder, is provided with at least two place's vacuum exhaust devices, and vacuum tightness is more than 0.08.
The invention has the beneficial effects as follows: the present invention is by controlling oligopolymer and the residual single total amount in graft ratio and the san copolymer of grafted ABS polymkeric substance and extruding vacuum tightness in mixing process and prepare excellent plating ABS resin compositions of thermostability and electrodepositable.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.Following examples will contribute to those skilled in the art further to understand the present invention, but not limit in any form the present invention.It should be pointed out that to those skilled in the art, without departing from the inventive concept of the premise, can also make some distortion and improvement.These all belong to protection scope of the present invention.
The invention discloses a kind of electroplating ABS resin combination and preparation method thereof, comprise that weight percentage is the san copolymer that 20～50% grafted ABS polymkeric substance and weight percentage are 50～80%, the graft ratio of described grafted ABS polymkeric substance is 45%～75%, and in san copolymer, the residual list of styrene monomer and acrylonitrile monemer composition and oligopolymer total amount are lower than 5000ppm.
The weight percentage of the divinyl in described grafted ABS polymkeric substance is 40～70%, and the median size of divinyl is 200～350nm, and divinyl rubber degree of crosslinking is 75～95%; The weight percentage of vinyl cyanide is 5～20%; Cinnamic weight percentage is 15～40%.
The relative molecular mass of described san copolymer is 40000～400000g/mol, and the weight percentage of vinyl cyanide is 15～35%.
Above-mentioned electroplating ABS resin combination adopts following methods to make:
(1) prepare respectively the step of grafted ABS polymkeric substance and san copolymer;
(2) the grafted ABS polymkeric substance, san copolymer and the heat-resistant agent that prepare and auxiliary agent are mixed to 30min in proportion in high-speed mixer;
(3) above-mentioned mixed mixture is entered from the main feeding of twin screw extruder, through melt extruding, cooling, dry, pelletizing obtains sample.
In step (1), the preparation method of grafted ABS polymkeric substance comprises the steps: taking uncle-lauryl mercaptan as molecular chain transfer agent, benzoyl peroxide is initiator, polybutadiene rubber is dissolved in vinylbenzene, acrylonitrile monemer and ethyl benzene solvent completely, temperature of reaction is 100 DEG C, controls the graft ratio of ABS graftomer by controlling the ratio of polybutadiene rubber and styrene-propene nitrile monomer.San copolymer by the styrene monomer mixing Diisopropyl azodicarboxylate of the acrylonitrile monemer of 15～35 weight parts, 65～85 weight parts, tert-dodecyl mercaptan via mass polymerization and remove volatile component and make.
(2) grafted ABS polymkeric substance, san copolymer, heat-resistant agent and other auxiliary agents are fully mixed in high-speed mixer to 30min, wherein grafted ABS polymkeric substance and san copolymer are pressed 1:4～1:1 feeding;
(3) above-mentioned mixed mixture is entered from the main feeding of twin screw extruder, through melt extruding, cooling, dry, pelletizing obtains sample.Wherein, twin screw extruder has ten temperature control regions, and temperature is made as 210～230 DEG C, and two vacuumize position and are arranged at respectively the 4th He 9th district, and vacuum tightness is 0.09MPa.
Carry out extruding pelletization according to above-mentioned preparation method, have 8 embodiment, by material at 80 DEG C of dry 12h, ensure water-intake rate <0.05%, then injection moulding under same injecting condition, carries out corresponding physical property measurement and applicating evaluating analysis, sees the following form 1.
Physical property measurement: based on the melt flow rate (MFR) (MFR) of ASTM D1238 standard testing resin, test condition is 220 DEG C of * 10kg; Based on ASTM D256 standard test Izod (1/8 ") notched Izod impact strength, see the following form 1.
Evaluation of Thermal Stability: will be dried sufficient resin combination and become 90*140*3.2mm through injection molding
3large high tabula rasa, injection temperature is set to 230 DEG C, heat is 0min and 10min the residence time.Observe its foxy (△ YI), the thermostability of the lower expression resin combination of △ YI value is better, sees the following form 1.
Electroplate yield: the large high tabula rasa completing under same electroplating technology being carried out to warm the depositing after experiment of height of 90 DEG C of * 24h, whether have bubbly defect, see the following form 1 if observing high light electroplate surface.
Table 1
Can find out from experimental result, in the formula system of electroplating ABS resin combination, select the grafted ABS polymkeric substance with specific graft ratio, the moulding yield of the corresponding ABS resin making and plating yield obviously promote.Comparative example 1～5, in the situation that each component is equivalent weight proportioning, after the ABS resin composition of embodiment 2～4 stops through 230 DEG C of heat, foxy is little, plating yield is high, and after the ABS resin composition of the higher embodiment 5 of the lower embodiment 1 of graft ratio and graft ratio stops through 230 DEG C of heat, foxy is larger, electroplates yield low; Comparative example 7 and 8, reduce oligopolymer and residual single total amount of san copolymer, and after ABS resin composition stops through 230 DEG C of heat, foxy is less.Visible, the formability and the electrodepositable that improve plating ABS resin by oligopolymer and residual single total amount in the graft ratio in control grafted ABS polymkeric substance and control san copolymer are effective and feasible.
Above specific embodiments of the invention are described.It will be appreciated that, the present invention is not limited to above-mentioned specific implementations, and those skilled in the art can make various distortion or amendment within the scope of the claims, and this does not affect flesh and blood of the present invention.
Claims (9)
1. an electroplating ABS resin combination, it is characterized in that, comprise that weight percentage is the san copolymer that 20～50% grafted ABS polymkeric substance and weight percentage are 50～80%, the graft ratio of described grafted ABS polymkeric substance is 45%～75%, and in san copolymer, the residual list of styrene monomer and acrylonitrile monemer composition and oligopolymer total amount are lower than 5000ppm.
2. electroplating ABS resin combination according to claim 1, it is characterized in that, the weight percentage of the divinyl in described grafted ABS polymkeric substance is 40～70%, and the median size of divinyl is 200～350nm, and divinyl rubber degree of crosslinking is 75～95%; The weight percentage of vinyl cyanide is 5～20%; Cinnamic weight percentage is 15～40%.
3. electroplating ABS resin combination according to claim 1, is characterized in that, the relative molecular mass of described san copolymer is 40000～400000g/mol, and the weight percentage of vinyl cyanide is 15～35%.
4. a preparation method for electroplating ABS resin combination as claimed in claim 1, is characterized in that, comprises the steps:
(1) prepare respectively the step of grafted ABS polymkeric substance and san copolymer;
(2) step of the grafted ABS polymkeric substance, san copolymer and the heat-resistant agent that prepare and auxiliary agent being mixed to 30min in proportion in high-speed mixer;
(3) above-mentioned mixed mixture is entered from the main feeding of twin screw extruder, through the step melt extruding, cooling, dry, pelletizing obtains sample.
5. the preparation method of electroplating ABS resin combination according to claim 4, it is characterized in that, the described middle grafted ABS polymkeric substance of step (1) is under divinyl rubber emulsion exists, mix tertiary lauryl mercaptan with styrene monomer, acrylonitrile monemer and benzoyl peroxide carries out graft polymerization, then make through condensing, dewater, after dry; Described san copolymer by the styrene monomer mixing Diisopropyl azodicarboxylate of the acrylonitrile monemer of 15～35 weight parts, 65～85 weight parts, tert-dodecyl mercaptan via mass polymerization and remove volatile component and make.
6. the preparation method of electroplating ABS resin combination according to claim 5, it is characterized in that, described divinyl rubber emulsion is to be aggregated in advance after the small particle size rubber latex of 0.07～0.15 μ m by divinylic monomer, then with the method for pressure agglomeration, the small particle size rubber hypertrophy of 0.07～0.15 μ m is become to the rubber latex of 0.2～0.35 μ m.
7. the preparation method of electroplating ABS resin combination according to claim 4, is characterized in that, in step (2), grafted ABS polymkeric substance and san copolymer are pressed 1:4～1:1 mixing.
8. the preparation method of electroplating ABS resin combination according to claim 4, is characterized in that, in step (3), twin screw extruder is prepared the resin of particle form under 210～230 DEG C of processing temperatures.
9. the preparation method of electroplating ABS resin combination according to claim 8, is characterized in that, be provided with at least two place's vacuum exhaust devices, and vacuum tightness is more than 0.08 in the machine barrel of twin screw extruder.
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| CN201410186859.6A CN104004313A (en) | 2014-05-05 | 2014-05-05 | ABS resin composition for electroplating and preparation method thereof |
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| CN201410186859.6A CN104004313A (en) | 2014-05-05 | 2014-05-05 | ABS resin composition for electroplating and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114479300A (en) * | 2020-11-12 | 2022-05-13 | 中国石油天然气股份有限公司 | Electroplating-grade ABS resin composition, electroplating-grade ABS resin and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1365985A (en) * | 2000-12-27 | 2002-08-28 | 大科能树脂有限公司 | Thermoplastic rsin composition and its product |
| CN103342864A (en) * | 2013-07-19 | 2013-10-09 | 上海锦湖日丽塑料有限公司 | Electroplating ABS (Acrylonitrile Butadiene Styrene) resin with high binding force and preparation method thereof |
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- 2014-05-05 CN CN201410186859.6A patent/CN104004313A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1365985A (en) * | 2000-12-27 | 2002-08-28 | 大科能树脂有限公司 | Thermoplastic rsin composition and its product |
| CN103342864A (en) * | 2013-07-19 | 2013-10-09 | 上海锦湖日丽塑料有限公司 | Electroplating ABS (Acrylonitrile Butadiene Styrene) resin with high binding force and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114479300A (en) * | 2020-11-12 | 2022-05-13 | 中国石油天然气股份有限公司 | Electroplating-grade ABS resin composition, electroplating-grade ABS resin and preparation method thereof |
| CN114479300B (en) * | 2020-11-12 | 2024-03-26 | 中国石油天然气股份有限公司 | Electroplating-grade ABS resin composition, electroplating-grade ABS resin and preparation method thereof |
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Application publication date: 20140827 |