CN111073150A - Dimensionally stable electroplatable polypropylene composite material and preparation method thereof - Google Patents
Dimensionally stable electroplatable polypropylene composite material and preparation method thereof Download PDFInfo
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- CN111073150A CN111073150A CN201911411147.9A CN201911411147A CN111073150A CN 111073150 A CN111073150 A CN 111073150A CN 201911411147 A CN201911411147 A CN 201911411147A CN 111073150 A CN111073150 A CN 111073150A
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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
- C08L23/12—Polypropene
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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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- 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
- C08K2201/005—Additives being defined by their particle size in general
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- 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
- C08K2201/011—Nanostructured additives
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
The invention discloses a preparation method of a polypropylene composite material with stable size and capable of being electroplated, which comprises the following components in percentage by mass: 17.1-99.5% of polypropylene; random copolymerized polypropylene: 0 to 20 percent; 0-20% of a filler; electroplating additive: 0 to 20 percent; a toughening agent: 0-20%, nucleating agent: 0 to 1 percent; 10100.1-0.3% of antioxidant; 0.1-0.3% of antioxidant DSTP; 1680.1-0.3% of antioxidant; 70720.1-0.5% of an auxiliary agent; 0.1-0.5% of auxiliary agent-CaST; the invention has the beneficial effects that: the invention solves the problem of poor dimensional stability of the polypropylene material by the design of the formula and the selection of the base material, the filler and the auxiliary agent, and the plating additive is added into the material formula, and the plating additive is a weakly alkaline filler added into the polypropylene material, so that the surface of the polypropylene material can be coarsened by an acidic solution, the feasibility of plating is realized, and the realization of plating of the polypropylene material has important significance for increasing the application of the polypropylene as the appearance.
Description
Technical Field
The invention relates to a preparation method of a polypropylene composite material with stable size and capable of being electroplated, wherein the polypropylene material is used for appearance parts and mainly meets the requirements of appearance through color matching, paint spraying and other modes. .
Background
The polypropylene is widely applied to the fields of automobiles, household appliances, buildings, fibers, daily necessities and the like as general plastic, has small density, is one of the lightest varieties of the plastic, has good mechanical property and higher heat resistance, the use temperature of the modified polypropylene material can reach 110-120 ℃, and in addition, the polypropylene has no water absorption, no toxicity and excellent electrical insulation property. However, polypropylene materials are poor in cold resistance, are liable to be aged under the action of light and heat, are poor in coloring properties and are liable to burn, and polypropylene materials are usually subjected to material modification before use in accordance with the use requirements.
In order to realize the problem of light weight, thinness, shortness and shortness of products, the market demand of plastic electroplating is on a trend of rising year by year, because ABS materials have the characteristics of good dimensional stability, excellent processing and forming and easy plating, more than 90 percent of the electroplating plastics are ABS and alloy materials thereof, the requirements of electroplating products on high heat resistance, impact resistance and the like are increasingly increased, the requirements of electroplating engineering plastics such as nylon resin, polyphenyl ether resin, polyacetal resin and the like are increasingly increased, the requirements of electroplating products on smooth appearance electroplating surfaces of the electroplating plastics are high, and the high bonding force of the electroplating layers is a basic requirement of the electroplating quality of plastic parts.
The polypropylene material has the advantages of low price, excellent performance and the like, is the most widely applied general plastic at present, but the polypropylene material has fewer cases when being applied to electroplating plastics due to the problem that the polypropylene material is difficult to electroplate due to the characteristics of the material, and has positive significance for meeting the electroplating requirements through material modification, namely the application and popularization of the polypropylene material and the development of the electroplating plastics.
Disclosure of Invention
The invention provides a preparation method of a polypropylene composite material with stable size and capable of being electroplated, which realizes that the polypropylene material meets the requirement of electroplating by material selection and formula design, and the feasibility of the size stability and the surface roughening of the polypropylene material.
In order to solve the technical problems, the invention adopts the technical scheme that:
a preparation method of a dimensionally stable electroplatable polypropylene composite material comprises the following raw materials in percentage by weight:
the polypropylene melt index is 5-60g/10min (230 ℃, 2.16 kg).
The polypropylene can be homopolymerized polypropylene or polypropylene, and the melt index is 5-60g/10min (230 ℃, 2.16 kg).
The random copolymerization polypropylene has low crystallinity and high dimensional stability, and can play a role in increasing the dimensional stability when added into an electroplating polypropylene formula.
The modified filling mineral can be talcum powder, and the particle size is as follows: 10000 meshes, and the high-mesh filler is beneficial to improving the dimensional stability of the polypropylene material and reducing secondary shrinkage. .
The nucleating agent is a nano-coated silicon dioxide nucleating agent, has high nucleating efficiency, enables a polypropylene material to be fully crystallized in an injection molding stage, reduces secondary shrinkage, and increases dimensional stability.
The antioxidant is a mixture of 1010/DSTP/168/7072.
The toughening agent is ethylene-octene copolymer (POE), and can effectively increase the toughness of the polypropylene material.
The electroplating additive is wollastonite with weakly alkaline surface coated with a coupling agent, and the particle size of the wollastonite is (D50): 4 μm, pH: 8-9, the electroplating additive migrates to the surface of the injection molding in the injection molding process, the electroplating additive is weakly alkaline and has a small particle size, pits can be formed on the surface of the injection molding through coarsening of the acid liquor, and the peeling strength of an electroplated layer is increased.
The invention provides a preparation method of a polypropylene composite material with stable size and capable of being electroplated, which comprises the following steps:
(1) weighing polypropylene, random copolymerization polypropylene, a toughening agent, an antioxidant 1010, an antioxidant DSTP, an antioxidant 168, an auxiliary agent-7072, an auxiliary agent-CAST and a nucleating agent according to a formula ratio; uniformly mixing the components by a high-speed stirrer for later use; the filler and the electroplating additive are taken according to the ratio of the formula for standby.
(2) And adding the mixed raw materials into a double-screw extruder through a main feeding port, adding the filler and the electroplating additive through a side feeding port, and performing melt extrusion, granulation, drying treatment and other processes to obtain the light absorption component polypropylene material.
Compared with the prior art, the invention has the advantages that: the invention increases the dimensional stability of the polypropylene material through the formula design of multiple dimensions such as base materials, fillers, auxiliary agents and the like, and simultaneously, the alkalescent electroplating additive is added in the material formula, so that the polypropylene material can be roughened in an acid solution, the feasibility of electroplating the polypropylene material is realized, the electroplated polypropylene is blank in the market, the process of the invention is simple, the electroplating can be realized according to the process of electroplating ABS, and the invention has positive significance for the application and popularization of the polypropylene material and the development of electroplated plastics.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention clearer, the present invention will be described in further detail with reference to specific embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The specific embodiment of the invention selects the following materials:
random copolymerized polypropylene A (PP-A), PP673K, SABIC
Polypropylene resin B (PP-B): melt index 30, test conditions 230 ℃ 2.16 kg;
polypropylene resin C (PP-C): melt index 50, test conditions 230 ℃ 2.16 kg;
talc powder: 10000 mesh, commercially available;
a toughening agent: POE-168, commercially available;
antioxidant 1010: hindered phenolic antioxidants, CIBA, switzerland;
β' -thiodipropionic acid distearate, a commercial antioxidant DSTP;
antioxidant 168: phosphite antioxidants, commercially available;
auxiliary agent-7072: henscman chemical engineering;
auxiliary agent calcium stearate CaST: is sold on the market;
nucleating agent: NanOsil ASD, Energy Strategy Associates Inc.
Electroplating additive: wollastonite particle diameter (D50): 4 μm, pH: 8-9, commercially available;
the product performance testing method comprises the following steps:
tensile property: according to ISO 527 method, spline size: 170 × 10 × 4mm, speed 50 mm/min.
Bending property: according to ISO178 method, spline size: 80 x 10 x 4mm, test speed 2 mm/min.
Notched impact strength: according to ISO 179 method, spline size: 80 x 10 x 4 mm.
Combustion residue: ISO 3451 method.
Evaluation of plating appearance: size of material sample plate: 150 x 100 x 3.2mm, appearance effect was evaluated by degreasing, roughening, neutralizing, sensitizing, activating, dispergating and chemical nickel
Surface roughening evaluation of the element: and visually evaluating the size, the morphology and the distribution of the roughened pits of the element piece, wherein the roughened pits are uniform in size and are in an inverted buckle shape, so that electroplating is facilitated.
Example 1:
weighing 2.0kg of PP-A, 1.0kg of PP-B, 2.1kg of PP-C, 1.7kg of POE, 100g of nucleating agent, 101010g of antioxidant, 10g of antioxidant DSTP and 16820 g of antioxidant; 10g of assistant calcium stearate (CaST), 707250 g of assistant, and uniformly mixing in a high-speed stirrer to obtain a mixture for later use; weighing 1.5kg of talcum powder and 1.5kg of electroplating additive for later use
Adding the mixture into a double-screw extruder (the length-diameter ratio of the extruder is 36 and the diameter of the screw is 35mm) through a main feeding port, adding fillers into the extruder through side feeding, controlling the temperature of each section of the double-screw extruder (from the feeding port to a head outlet) to be 180 ℃, 200 ℃, 220 ℃, 210 ℃ and the rotating speed of the double-screw extruder to be 500r/min, cooling extruded strips through a water tank, drying the extruded strips through a blast dryer, and cutting the extruded strips into particles to obtain the product.
The above materials were dried in a forced air drying cabinet at 100 ℃ for 2h and then injection molded into standard bars at a temperature of 230 ℃. And (3) testing the injection-molded mechanical property sample strip in a standard laboratory environment (23 ℃, 50% RH) after the state is adjusted for 24h, and performing visual evaluation after roughening and electroplating on the surface of the material piece and electroplating appearance evaluation according to the electroplating flow.
Example 2:
weighing 2.0kg of PP-A, 1.0kg of PP-B, 2.1kg of PP-C, 1.7kg of POE, 100g of nucleating agent, 101010g of antioxidant, 10g of antioxidant DSTP and 16820 g of antioxidant; 10g of assistant calcium stearate (CaST), 707250 g of assistant, and uniformly mixing in a high-speed stirrer to obtain a mixture for later use; weighing 1.0kg of talcum powder and 2.0kg of electroplating additive for later use
Adding the mixture into a double-screw extruder (the length-diameter ratio of the extruder is 36 and the diameter of the screw is 35mm) through a main feeding port, adding fillers into the extruder through side feeding, controlling the temperature of each section of the double-screw extruder (from the feeding port to a head outlet) to be 180 ℃, 200 ℃, 220 ℃, 210 ℃ and the rotating speed of the double-screw extruder to be 500r/min, cooling extruded strips through a water tank, drying the extruded strips through a blast dryer, and cutting the extruded strips into particles to obtain the product.
The above materials were dried in a forced air drying cabinet at 100 ℃ for 2h and then injection molded into standard bars at a temperature of 230 ℃. And (3) testing the injection-molded mechanical property sample strip in a standard laboratory environment (23 ℃, 50% RH) after the state is adjusted for 24h, and performing visual evaluation after roughening and electroplating on the surface of the material piece and electroplating appearance evaluation according to the electroplating flow.
Example 3:
weighing 2.0kg of PP-A, 1.0kg of PP-B, 2.1kg of PP-C, 1.7kg of POE, 100g of nucleating agent, 101010g of antioxidant, 10g of antioxidant DSTP and 16820 g of antioxidant; 10g of assistant calcium stearate (CaST), 707250 g of assistant, and uniformly mixing in a high-speed stirrer to obtain a mixture for later use; 0.5kg of talcum powder and 2.5kg of electroplating additive are weighed for later use
Adding the mixture into a double-screw extruder (the length-diameter ratio of the extruder is 36 and the diameter of the screw is 35mm) through a main feeding port, adding fillers into the extruder through side feeding, controlling the temperature of each section of the double-screw extruder (from the feeding port to a head outlet) to be 180 ℃, 200 ℃, 220 ℃, 210 ℃ and the rotating speed of the double-screw extruder to be 500r/min, cooling extruded strips through a water tank, drying the extruded strips through a blast dryer, and cutting the extruded strips into particles to obtain the product.
The above materials were dried in a forced air drying cabinet at 100 ℃ for 2h and then injection molded into standard bars at a temperature of 230 ℃. And (3) testing the injection-molded mechanical property sample strip in a standard laboratory environment (23 ℃, 50% RH) after the state is adjusted for 24h, and performing visual evaluation after roughening and electroplating on the surface of the material piece and electroplating appearance evaluation according to the electroplating flow.
Example 4:
weighing 2.0kg of PP-A, 1.0kg of PP-B, 2.1kg of PP-C, 1.7kg of POE, 100g of nucleating agent, 101010g of antioxidant, 10g of antioxidant DSTP and 16820 g of antioxidant; 10g of assistant calcium stearate (CaST), 707250 g of assistant, and uniformly mixing in a high-speed stirrer to obtain a mixture for later use; weighing 3.0kg of electroplating additive for later use
Adding the mixture into a double-screw extruder (the length-diameter ratio of the extruder is 36 and the diameter of the screw is 35mm) through a main feeding port, adding fillers into the extruder through side feeding, controlling the temperature of each section of the double-screw extruder (from the feeding port to a head outlet) to be 180 ℃, 200 ℃, 220 ℃, 210 ℃ and the rotating speed of the double-screw extruder to be 500r/min, cooling extruded strips through a water tank, drying the extruded strips through a blast dryer, and cutting the extruded strips into particles to obtain the product.
The above materials were dried in a forced air drying cabinet at 100 ℃ for 2h and then injection molded into standard bars at a temperature of 230 ℃. And (3) testing the injection-molded mechanical property sample strip in a standard laboratory environment (23 ℃, 50% RH) after the state is adjusted for 24h, and performing visual evaluation after roughening and electroplating on the surface of the material piece and electroplating appearance evaluation according to the electroplating flow.
Example 5:
weighing 2.0kg of PP-A, 2.1kg of PP-B, 1.0kg of PP-C, 1.7kg of POE, 100g of nucleating agent, 101010g of antioxidant, 10g of antioxidant DSTP and 16820 g of antioxidant; 10g of assistant calcium stearate (CaST), 707250 g of assistant, and uniformly mixing in a high-speed stirrer to obtain a mixture for later use; weighing 3.0kg of electroplating additive for later use
Adding the mixture into a double-screw extruder (the length-diameter ratio of the extruder is 36 and the diameter of the screw is 35mm) through a main feeding port, adding fillers into the extruder through side feeding, controlling the temperature of each section of the double-screw extruder (from the feeding port to a head outlet) to be 180 ℃, 200 ℃, 220 ℃, 210 ℃ and the rotating speed of the double-screw extruder to be 500r/min, cooling extruded strips through a water tank, drying the extruded strips through a blast dryer, and cutting the extruded strips into particles to obtain the product.
The above materials were dried in a forced air drying cabinet at 100 ℃ for 2h and then injection molded into standard bars at a temperature of 230 ℃. And (3) testing the injection-molded mechanical property sample strip in a standard laboratory environment (23 ℃, 50% RH) after the state is adjusted for 24h, and performing visual evaluation after roughening and electroplating on the surface of the material piece and electroplating appearance evaluation according to the electroplating flow.
Example 6:
weighing 1.0kg of PP-A, 1.0kg of PP-B, 3.1kg of PP-C, 1.7kg of POE, 100g of nucleating agent, 101010g of antioxidant, 10g of antioxidant DSTP and 16820 g of antioxidant; 10g of assistant calcium stearate (CaST), 707250 g of assistant, and uniformly mixing in a high-speed stirrer to obtain a mixture for later use; weighing 3.0kg of electroplating additive for later use
Adding the mixture into a double-screw extruder (the length-diameter ratio of the extruder is 36 and the diameter of the screw is 35mm) through a main feeding port, adding fillers into the extruder through side feeding, controlling the temperature of each section of the double-screw extruder (from the feeding port to a head outlet) to be 180 ℃, 200 ℃, 220 ℃, 210 ℃ and the rotating speed of the double-screw extruder to be 500r/min, cooling extruded strips through a water tank, drying the extruded strips through a blast dryer, and cutting the extruded strips into particles to obtain the product.
The above materials were dried in a forced air drying cabinet at 100 ℃ for 2h and then injection molded into standard bars at a temperature of 230 ℃. And (3) testing the injection-molded mechanical property sample strip in a standard laboratory environment (23 ℃, 50% RH) after the state is adjusted for 24h, and performing visual evaluation after roughening and electroplating on the surface of the material piece and electroplating appearance evaluation according to the electroplating flow.
Comparative example 1:
weighing 2.0kg of PP-A, 1.0kg of PP-B, 2.1kg of PP-C, 1.7kg of POE, 100g of nucleating agent, 101010g of antioxidant, 10g of antioxidant DSTP and 16820 g of antioxidant; 10g of assistant calcium stearate (CaST), 707250 g of assistant, and uniformly mixing in a high-speed stirrer to obtain a mixture for later use; weighing 3.0kg of talcum powder for later use
Adding the mixture into a double-screw extruder (the length-diameter ratio of the extruder is 36 and the diameter of the screw is 35mm) through a main feeding port, adding fillers into the extruder through side feeding, controlling the temperature of each section of the double-screw extruder (from the feeding port to a head outlet) to be 180 ℃, 200 ℃, 220 ℃, 210 ℃ and the rotating speed of the double-screw extruder to be 500r/min, cooling extruded strips through a water tank, drying the extruded strips through a blast dryer, and cutting the extruded strips into particles to obtain the product.
The above materials were dried in a forced air drying cabinet at 100 ℃ for 2h and then injection molded into standard bars at a temperature of 230 ℃. And (3) testing the injection-molded mechanical property sample strip in a standard laboratory environment (23 ℃, 50% RH) after the state is adjusted for 24h, and performing visual evaluation after roughening and electroplating on the surface of the material piece and electroplating appearance evaluation according to the electroplating flow.
Table 1: and (5) performance test results.
The data in the table 1 show that the electroplating additive in the material formula is alkalescent, pits with uniform size and inverted buckles can be formed on the surface of the surface under the etching action of the acid electrolyte, the electroplating feasibility of the polypropylene material is endowed, the electroplated polypropylene has good appearance, the crystallinity of the polypropylene material can be reduced by adding the random copolymerization polypropylene, the dimensional stability is improved, the crystallization of the polypropylene material in the injection molding process is improved by adding the nucleating agent, and the problems of injection molding shrinkage and the like caused by secondary crystallization are avoided.
Claims (8)
1. A dimensionally stable, electroplatable polypropylene composite characterized by: the composite material comprises the following raw materials in percentage by weight:
2. a dimensionally stable, electroplatable polypropylene composite according to claim 1, wherein: the polypropylene melt index is 5-60g/10min (230 ℃, 2.16 kg).
3. A dimensionally stable, electroplatable polypropylene composite according to claim 1, wherein: the toughening agent is an ethylene-octene copolymer (POE).
4. A dimensionally stable, electroplatable polypropylene composite according to claim 1, wherein: the modified filling mineral can be talcum powder, and the particle size is as follows: 10000 meshes.
5. A dimensionally stable, electroplatable polypropylene composite according to claim 1, wherein: the nucleating agent is a nano-coating silicon dioxide nucleating agent.
6. A dimensionally stable, electroplatable polypropylene composite according to claim 1, wherein: the antioxidant is a mixture of 1010/DSTP/168/7072.
7. A dimensionally stable, electroplatable polypropylene composite material according to claim 1 wherein said electroplating additive is wollastonite coated with a coupling agent to render the surface weakly basic, having a particle size (D50): 4 μm, pH: 8-9, the electroplating additive migrates to the surface of the injection molding in the injection molding process, the electroplating additive is weakly alkaline and has a small particle size, pits can be formed on the surface of the injection molding through coarsening of the acid liquor, and the peeling strength of an electroplated layer is increased.
8. A process for preparing a dimensionally stable, electroplatable polypropylene composite as claimed in any one of claims 1 to 7, wherein: the method comprises the following steps:
(1) weighing polypropylene, random copolymerization polypropylene, a toughening agent, an antioxidant 1010, an antioxidant DSTP, an antioxidant 168, an auxiliary agent-7072, an auxiliary agent-CAST and a nucleating agent according to a formula ratio; uniformly mixing the components by a high-speed stirrer for later use; taking the filler and the electroplating additive according to the ratio of the formula for later use;
(2) and adding the mixed raw materials into a double-screw extruder through a main feeding port, adding the filler and the electroplating additive through a side feeding port, and performing melt extrusion, granulation, drying treatment and other processes to obtain the light absorption component polypropylene material.
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