CN106280012A - A kind of plating polypropylene alloy material and preparation method thereof - Google Patents
A kind of plating polypropylene alloy material and preparation method thereof Download PDFInfo
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- CN106280012A CN106280012A CN201510321258.6A CN201510321258A CN106280012A CN 106280012 A CN106280012 A CN 106280012A CN 201510321258 A CN201510321258 A CN 201510321258A CN 106280012 A CN106280012 A CN 106280012A
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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
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
-
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- 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
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- 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)
- Electroplating Methods And Accessories (AREA)
Abstract
The invention discloses a kind of plating polypropylene alloy material and preparation method thereof, it is by polypropylene 620-700 part, acrylonitrile-butadiene-styrene copolymer 50-80 part, compatilizer 10-50 part, inorganic filler 200-300 part, antioxidant 4-8 part, lubricant 4-6 part, bridging agent 2-3 part is blended, extruding pelletization is prepared from.Plating polypropylene alloy material prepared by the present invention has good Plating appearance and coating strength, can reduce cost, and can replacing electroplating ABS；And improve the adhesive force between plating polypropylene plastic and coating, reduce part weight, improve its heat resistance.
Description
Technical field
The present invention relates to technical field of polymer materials, specifically a kind of plating polypropylene alloy material and preparation method thereof.
Background technology
Along with developing rapidly of industry, the application of plastic electroplating is increasingly extensive becomes one of important means of incrustation in plastic product.Compared with metallic article, plastic electroplating goods are possible not only to realize good metal-like, and can alleviate product weight, be effectively improved plastics outward appearance and ornamental while, also improve its performance at the aspect such as electric, hot and anti-corrosion, improve its surface mechanical strength.But the factors such as selection drawing abillity to be considered, the complexity of plating and the dimensional accuracy of plating plastic material.
The plastic product that may be used for plating at present almost can only select ABS material, but because of its architectural characteristic, it is impossible to meet the mechanical properties such as impact strength, hot strength, bending modulus simultaneously；And ABS material cost remains high always.And polypropylene (Polypropylene, it is called for short PP) it is a kind of hemicrystalline thermoplastic, it is cheap, also intensity and mechanical property requirements can be met, and anti-multiple organic solvent and acid and alkali corrosion, but because its degree of crystallinity is higher, surface coarsening is relatively difficult, coating adhesion is poor, it is difficult to obtain application in the product needing plating.
Summary of the invention
The present invention is directed to shortcoming and problem that above prior art exists, one plating polypropylene alloy material and preparation method thereof is provided, this PP material can directly replace ABS material to be used for Electroplating articles, reduce material cost, meet mechanical property requirements, Injection moulded part recoverable, the production of this material simultaneously has the advantages that technique is simple, production efficiency is high.
The technical scheme is that
A kind of plating polypropylene alloy material, is prepared from by weight by following components:
Polypropylene (PP)
620-700 part
Acrylonitrile-butadiene-styrene copolymer (ABS)
50-80 part
Compatilizer
10-50 part
Inorganic filler
200-300 part
Antioxidant
4-8 part
Lubricant
4-6 part
Bridging agent
2-3 part.
Described acrylic resin is homopolymerization or COPP, and its melt index under temperature 230 DEG C, test load 2.16Kg is 8-20g/10min.
In described ABS resin, the mass fraction of butadiene is more than 65%, and its melt index under temperature 220 DEG C, test load 10Kg is 15-25g/10min；Butadiene content in this ABS requires, more than 65%, to belong to SAN-g-PB, on the one hand can improve toughness and the intensity of PP alloy material, can reduce the degree of crystallinity of polypropylene material, in order to roughening treatment during plating simultaneously.The additionally addition of SAN-g-PB, it is also possible to improve the polarity of polypropylene material, improves the adhesive strength of coating and acrylic resin.
Described compatilizer is maleic anhydride inoculated polypropylene (PP-g-MAH), and maleic anhydride grafting ratio is 0.5-1.0%, and the melt index under temperature 230 DEG C, test load 2.16Kg is 80-120g/10min
Described inorganic filler be particle diameter be the thing mixed above of the one or two kinds of in the zinc oxide of 5-7 micron, titanium dioxide, calcium carbonate, barium sulfate.
Described antioxidant is that the double octadecyl (antioxidant DSTDP) of four [β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester (antioxidant 1010), three [2.4-di-tert-butyl-phenyl] phosphite ester (irgasfos 168) and thio-2 acid is by weight the composite antioxidant for 1:1:2 composition.Wherein antioxidant 1010 is a kind of polynary hindered phenol type antioxidant, and irgasfos 168 is phosphoric acid ester auxiliary antioxidant, has the effect preventing the course of processing from degrading；Antioxidant DSTDP is monothioester class auxiliary antioxidant, compound with phenols primary antioxidant, ageing stability and light stability can be strengthened, above-mentioned three kinds of antioxidant compounding according to 1:1:2, it is possible not only to prevent the degraded in extruding pelletization and injection mo(u)lding aging, moreover it is possible to provide the most stable anti-heat oxygen aging resistance and weathering performance, beyond this antioxidant compound proportion, or cause cost to increase, or affect heat resistance and the weather resistance of system.
Described lubricant one in ethylene bis stearamide (EBS), calcium stearate, silicone powder.
Described bridging agent is isopropyl three (isostearoyl base) titanate esters or isopropyl two (methylacryloyl) isostearoyl base titanate esters; it is to process for the surface of inorganic filler; increase the hydrophobicity of filler, dispersibility; the mechanical performance of material can be improved; particularly shock strength, can reduce the melt viscosity of composite simultaneously.
The preparation method of described plating polypropylene alloy material comprises the following steps:
(1) raw material is dry: ABS is dried at 80-90 DEG C 2-3h；
(2) mixing of raw material: join in homogenizer by 200-300 part inorganic filler, is subsequently adding bridging agent and the lubricant of 4-6 part of 2-3 part, mix and blend 4-6min at 40-60 DEG C；Then after being sequentially added into 620-700 part PP, 50-80 part ABS, 10-50 part compatilizer, 4-8 part antioxidant, mix and blend 5-15min under room temperature；
(3) extruding pelletization: be placed in double screw extruder by the material mixed, through fusion plastification, extrudes, cools down, pelletizing, obtains electroplating polypropylene alloy material；Double screw extruder used, screw diameter 40-65mm, the draw ratio of screw rod is 40:1, mixed melting temperature is set as: first paragraph 120-160 DEG C, second segment 160-180 DEG C, the 3rd section 180-200 DEG C, 4th section 190-210 DEG C, 5th section 210-230 DEG C, melt temperature 180-220 DEG C, head temperature 200-220 DEG C
The present invention compared with the existing technology, has the advantage that and beneficial effect:
1, the present invention propose process design reasonable, simple to operate, production efficiency is high, practical；
2, during the present invention selects ABS resin, butadiene content is more than 65%, belongs to SAN-g-PB, on the one hand can improve toughness and the intensity of PP alloy material, can reduce the degree of crystallinity of polypropylene material, in order to roughening treatment during plating simultaneously.The additionally addition of SAN-g-PB, it is also possible to improve the polarity of polypropylene material, improves the adhesive strength of coating and acrylic resin, fundamentally solves the problem that polypropylene product is difficult to electroplate.
3, the present invention adds bridging agent to process for the surface of inorganic filler, increase the hydrophobicity of filler, dispersibility；The addition of filler also reduces density of material, makes part weight reduce；Additionally can improve the mechanical performance of material, particularly shock strength, the melt viscosity of composite can be reduced simultaneously.
4, the present invention select suitable inorganic filler as acidification point, during the roughening treatment of plating, it is possible to use the chemical reaction between acid solution and inorganic filler produces the hole of specific dimensions.
5, the present invention selects three kinds of composite antioxidants, it is possible not only to prevent the degraded in extruding pelletization and injection mo(u)lding aging, also it is provided that the most stable anti-heat oxygen aging resistance and weathering performance, beyond this antioxidant compound proportion, or cause cost to increase, or affect heat resistance and the weather resistance of system.
6, the plating polypropylene alloy material that prepared by the present invention compared with prior art, improves the adhesive force between plating polypropylene plastic and coating, reduces part weight, improves its heat resistance.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is further illustrated, and the acrylic resin used in embodiment is COPP, and its melt index under temperature 230 DEG C, test load 2.16Kg is 15g/10min；
In ABS resin, the mass fraction of butadiene is 67%, and the melt index under temperature 220 DEG C, test load 10Kg is 20g/10min；
Compatilizer is maleic anhydride inoculated polypropylene (PP-g-MAH), and wherein maleic anhydride grafting ratio is 0.8%, and the melt index under temperature 230 DEG C, test load 2.16Kg is 110g/10min；
Inorganic filler be particle diameter be the thing mixed above of the one or two kinds of in the zinc oxide of 5-7 micron, titanium dioxide, calcium carbonate, barium sulfate；
Antioxidant is that the double octadecyl (antioxidant DSTDP) of four [β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester (antioxidant 1010), three [2.4-di-tert-butyl-phenyl] phosphite ester (irgasfos 168) and thio-2 acid is by weight the composite antioxidant for 1:1:2 composition；
Lubricant one in ethylene bis stearamide (EBS), calcium stearate, silicone powder；
Bridging agent is the one in isopropyl three (isostearoyl base) titanate esters or isopropyl two (methylacryloyl) isostearoyl base titanate esters.
Pressing noodle producing method and prepare embodiment 1-4 and comparative example 1-4, concrete formula is as shown in table 1 below:
(1) raw material is dry: ABS is dried at 80-90 DEG C 2-3h；
(2) mixing of raw material: join in homogenizer by 200-300 part inorganic filler, is subsequently adding bridging agent and the lubricant of 4-6 part of 2-3 part, mix and blend 4-6min at 40-60 DEG C；Then after being sequentially added into 620-700 part PP, 50-80 part ABS, 10-50 part compatilizer, 4-8 part antioxidant, mix and blend 5-15min under room temperature；
(3) extruding pelletization: be placed in double screw extruder by the material mixed, through fusion plastification, extrudes, cools down, pelletizing, obtains electroplating polypropylene alloy material；Double screw extruder used, screw diameter 40-65mm, the draw ratio of screw rod is 40:1, mixed melting temperature is set as: first paragraph 120-160 DEG C, second segment 160-180 DEG C, the 3rd section 180-200 DEG C, 4th section 190-210 DEG C, 5th section 210-230 DEG C, melt temperature 180-220 DEG C, head temperature 200-220 DEG C.
Being molded after being dried 6h in the plating polypropylene alloy material obtained in embodiment in an oven 90 DEG C of baking ovens, injection batten is ASTM batten, and injection temperature is as follows:
Blanking section: 180 DEG C；Second segment: 200 DEG C；3rd section: 220 DEG C；Nozzle: 210 DEG C；
Finally injection batten is put in exsiccator and carries out status adjustment: regulation temperature: 23 DEG C, regulating time: 24h；Each embodiment test result is as shown in table 2 below:
Table 2, each embodiment test result contrast
| ASTM | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Remarks |
| Hot strength (MPa) | 65 | 57 | 52 | 55 | 52 | 60 | 46 | 52 | |
| Bending strength (MPa) | 78 | 68 | 60 | 65 | 64 | 72 | 58 | 60 | |
| Bending modulus (MPa) | 3200 | 2600 | 2200 | 2400 | 3100 | 2980 | 1550 | 2450 | |
| Izod notched impact strength (KJ/m2) | 24 | 21 | 20 | 20 | 13 | 22 | 16 | 16 | 23℃ |
| Ash (%) | 30.1 | 25.0 | 20.1 | 20.3 | 30.2 | 30.1 | 10.2 | 25.0 | |
| Heat distortion temperature (DEG C) | 110 | 108 | 105 | 105 | 106 | 108 | 85 | 104 | 0.455MPa |
| Plating appearance | Well | Well | Well | Well | Poor | Poor | Well | Poor | |
| Coating strength | Well | Well | Well | Well | Poor | Poor | Poor | Poor |
As can be seen from Table 2, material prepared by embodiment 1-4 prepared by the present invention has good Plating appearance and coating strength, can reach to drop the effect of this replacing electroplating ABS.
From the test result of embodiment 1 and comparative example 1-2 it can be seen that owing to compatilizer (PP-g-MAH) can improve the compatibility of PP and ABS, improve the polarity of polypropylene and inorganic filler simultaneously.So being not added with compatilizer or ABS, then the electroplating effect of the material prepared does not reaches the level of replacing electroplating ABS, and its electroplating effect is poor.
From the test result of embodiment 1 and comparative example 3 it can be seen that the inorganic filler addition as electroplating processes hot spot less than 20%, can not be not enough to form limited hole in polypropylene alloy, and affect the intensity of coating otherwise when roughening treatment.
Can be seen that from the test result of embodiment 2 with comparative example 4, the bridging agent process to filling surface, the compatibility of resin and filler can be improved, improve the mechanical strength of its material, especially shock strength and hot strength, therefore electroplate in the system of PP, it is necessary to bridging agent, inorganic filler is carried out the surface process of necessity.
The above-mentioned description to embodiment is to be understood that for ease of those skilled in the art and apply the present invention.These embodiments obviously easily can be made various amendment by person skilled in the art, and General Principle described herein is applied in other embodiments without through performing creative labour.Therefore, the invention is not restricted to embodiment here, those skilled in the art should be within protection scope of the present invention according to the announcement of the present invention, the improvement made without departing from scope and amendment.
Claims (9)
1. a plating polypropylene alloy material, it is characterised in that be prepared from by weight by following components:
Polypropylene
620-700 part
Acrylonitrile-butadiene-styrene copolymer 50-80 part
Compatilizer
10-50 part
Inorganic filler
200-300 part
Antioxidant
4-8 part
Lubricant
4-6 part
Bridging agent
2-3 part.
A kind of plating polypropylene alloy material the most according to claim 1, it is characterised in that: described polypropylene is homopolymerization or COPP, and the melt index under temperature 230 DEG C, test load 2.16Kg is 8-20g/10min.
A kind of plating polypropylene alloy material the most according to claim 1, it is characterized in that: in described acrylonitrile-butadiene-styrene copolymer, the mass fraction of butadiene is more than 65%, and the melt index under temperature 220 DEG C, test load 10Kg is 15-25g/10min.
A kind of plating polypropylene alloy material the most according to claim 1, it is characterized in that: described compatilizer is maleic anhydride inoculated polypropylene (PP-g-MAH), wherein maleic anhydride grafting ratio is 0.5-1.0%, and the melt index under temperature 230 DEG C, test load 2.16Kg is 80-120g/10min.
A kind of plating polypropylene alloy material the most according to claim 1, it is characterised in that: described inorganic filler be particle diameter be at least one in the zinc oxide of 5-7 micron, titanium dioxide, calcium carbonate, barium sulfate.
A kind of plating polypropylene alloy material the most according to claim 1, it is characterized in that: described antioxidant is that the double octadecyl (antioxidant DSTDP) of four [β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester (antioxidant 1010), three [2.4-di-tert-butyl-phenyl] phosphite ester (irgasfos 168) and thio-2 acid is by weight for the composite antioxidant of 1:1:2 composition.
A kind of plating polypropylene alloy material the most according to claim 1, it is characterised in that: described lubricant is the one in ethylene bis stearamide (EBS), calcium stearate, silicone powder.
A kind of plating polypropylene alloy material the most according to claim 1, it is characterised in that: described bridging agent is isopropyl three (isostearoyl base) titanate esters or isopropyl two (methylacryloyl) isostearoyl base titanate esters.
9. the preparation method of the plating polypropylene alloy material as described in any one of claim 1-8, it is characterised in that: comprise the following steps:
(1) raw material drying: ABS is dried at 80-90 DEG C 2-3h；
(2) raw material mixing: 200-300 part inorganic filler is joined in homogenizer, is subsequently adding bridging agent and the lubricant of 4-6 part of 2-3 part, mix and blend 4-6min at 40-60 DEG C；Then, after being sequentially added into 620-700 part PP, 50-80 part ABS, 10-50 part compatilizer, 4-8 part antioxidant, under room temperature, mix and blend 5-15min is continued；
(3) extruding pelletization: be placed in double screw extruder by the material mixed, through fusion plastification, extrudes, cools down, pelletizing, obtains electroplating polypropylene alloy material；
The screw diameter 40-65mm of described double screw extruder, the draw ratio of screw rod are 40:1, mixed melting temperature is set as: first paragraph 120-160 DEG C, second segment 160-180 DEG C, the 3rd section 180-200 DEG C, the 4th section 190-210 DEG C, the 5th section 210-230 DEG C, melt temperature 180-220 DEG C, head temperature 200-220 DEG C.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108822404A (en) * | 2018-06-20 | 2018-11-16 | 罗国球 | A kind of PP composite material and preparation method thereof suitable for electroplating reaction |
| CN111793283A (en) * | 2020-07-22 | 2020-10-20 | 广东聚石化学股份有限公司 | Halogen-free flame-retardant PP/ABS alloy material and preparation method and application thereof |
| CN112759880A (en) * | 2020-12-25 | 2021-05-07 | 金发科技股份有限公司 | Electroplatable high-impact flame-retardant polypropylene material and preparation method and application thereof |
| CN115819883A (en) * | 2022-12-13 | 2023-03-21 | 金发科技股份有限公司 | Polypropylene composition easy to electroplate in water and preparation method and application thereof |
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| CN104312008A (en) * | 2014-10-21 | 2015-01-28 | 杭州泛亚卫浴股份有限公司 | High-brightness PP electroplating material and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108822404A (en) * | 2018-06-20 | 2018-11-16 | 罗国球 | A kind of PP composite material and preparation method thereof suitable for electroplating reaction |
| CN111793283A (en) * | 2020-07-22 | 2020-10-20 | 广东聚石化学股份有限公司 | Halogen-free flame-retardant PP/ABS alloy material and preparation method and application thereof |
| CN111793283B (en) * | 2020-07-22 | 2023-09-08 | 广东聚石化学股份有限公司 | Halogen-free flame-retardant PP/ABS alloy material and preparation method and application thereof |
| CN112759880A (en) * | 2020-12-25 | 2021-05-07 | 金发科技股份有限公司 | Electroplatable high-impact flame-retardant polypropylene material and preparation method and application thereof |
| CN115819883A (en) * | 2022-12-13 | 2023-03-21 | 金发科技股份有限公司 | Polypropylene composition easy to electroplate in water and preparation method and application thereof |
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Application publication date: 20170104 |