CN110951159B - Polypropylene/polyamide/polyketone composition and preparation method thereof - Google Patents
Polypropylene/polyamide/polyketone composition and preparation method thereof Download PDFInfo
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- CN110951159B CN110951159B CN201911269634.6A CN201911269634A CN110951159B CN 110951159 B CN110951159 B CN 110951159B CN 201911269634 A CN201911269634 A CN 201911269634A CN 110951159 B CN110951159 B CN 110951159B
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- 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
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
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- 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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Abstract
The invention provides a polypropylene/polyamide/polyketone composition and a preparation method thereof, wherein the polypropylene/polyamide/polyketone composition is prepared from the following raw materials: polypropylene resin, polyamide resin, polyketone resin, compatilizer, scratch-resistant agent, antioxidant and lubricant; the compatilizer is at least one of maleic anhydride grafted polypropylene and maleic anhydride grafted polyethylene; the scratch-resistant agent consists of cubic boron nitride and hexagonal boron nitride. The polypropylene/polyamide/polyketone composition has high hardness and excellent scratch resistance, and simultaneously has good mechanical properties.
Description
Technical Field
The invention belongs to the field of materials, and particularly relates to a polypropylene/polyamide/polyketone composition and a preparation method thereof.
Background
In recent years, in the field of home appliances such as air conditioners, refrigerators, small home appliances and the like, a large amount of polymer materials have been used as exterior articles, and although polymers have a good high-light effect, they have a limited hardness and a weak scratch resistance. Touch extrusion can inevitably appear in the transportation, and the wiping of surface dust all probably leads to the outward appearance to appear mar scheduling problem in the use, and the emergence of mar can greatly reduced consumer's use experience, also can reduce the actual life of relevant household electrical appliances. Therefore, the scratch resistance of the polymer material is improved, and the method has important practical significance in the field of household appliances.
Polyketone is a polymer material prepared by alternating copolymerization of carbon monoxide and one or more unsaturated monomers containing double bonds. It is of great industrial interest because of its excellent heat resistance, chemical resistance and wear resistance. Currently, a series of polyketone alloy materials are disclosed in the prior art, such as: chinese patent CN201710024474.3 discloses a polyamide/polyketone alloy material, which is prepared by blending polytetrafluoroethylene, silicone and molybdenum disulfide wear-resistant agent to obtain a scratch-resistant effect. Chinese patent 201710369133.X discloses a highly wear resistant polyamide/polyketone alloy using polyamide, polyketone, a compatibilizer, needle coke and other adjuvants to achieve wear resistance. Chinese patent CN201710158000.8 discloses a high-gloss scratch-resistant polyamide composition and a preparation method thereof, wherein a spherical branched amide functional auxiliary agent is matched with polyketone to obtain scratch resistance. Chinese patent CN201611072935.6 discloses an alloy material prepared using recycled PC and POK. Chinese patent CN201811491013 discloses an anti-pollution high-wear-resistance polypropylene material and a preparation method thereof, wherein the polypropylene material takes high-crystallization homopolymerization polypropylene as a basic component, polyketone resin is added to improve the wear resistance and mechanical property of the material, and organic group modified ultrahigh molecular weight polysiloxane is used as an anti-fouling agent to improve the water and oil resistance of an alloy material and improve the wear resistance of the material. Chinese patent CN201710615089.6 discloses an antistatic wear-resistant polypropylene composite material for electric commercial use, wherein the wear resistance is realized by boron nitride and MoSi2Molybdenum disulfide and LDPE carrier. Chinese patent CN201611108699.9 discloses a wear-resistant modified polybutylene terephthalate, the wear-resistant property of which is obtained by graphene, boron nitride and boron carbide. Chinese patent CN201611227099.4 discloses a wear-resistant antistatic polyamide composite material and a preparation method thereof, wherein the wear resistance of the composite material is improved by the synergistic effect of modified hexagonal boron nitride micro-sheets and silicon carbide capsules. Chinese patent CN201611017997.7 discloses hexagonal boron nitride epoxy corrosion-resistant and wear-resistantThe coating and the preparation method and application thereof are characterized in that at least part of aniline oligomer is combined with hexagonal boron nitride through physical action, so that the hexagonal boron nitride is uniformly dispersed in the coating, and a good wear-resistant effect is obtained. Chinese patent CN201420007202.9 discloses a heat-conducting wear-resistant filler, a preparation method thereof and a heat-conducting wear-resistant plastic-based composite material containing the heat-conducting wear-resistant filler, namely, a carbon nano tube and cubic boron nitride are compounded to prepare a heat-conducting wear-resistant filler-carbon nano tube-cubic boron nitride composite material, and the heat-conducting wear-resistant filler-carbon nano tube-cubic boron nitride composite material is used in plastics. Chinese patent CN201210426757.8 discloses a wear-resistant filler, a wear-resistant composite material prepared from the wear-resistant filler and a preparation method of the wear-resistant composite material. Chinese patent CN201710094975.9 discloses a scratch-resistant master batch, which is prepared by compounding ultra-high molecular weight polyethylene with specific number average molecular weight, cubic boron nitride with specific particle size and polyethylene grafted maleic anhydride with specific maleic anhydride grafting rate, and is added into a thermoplastic composite material, so that the wear resistance and scratch resistance of the prepared thermoplastic composite material are improved.
Disclosure of Invention
Based on the above, the invention aims to provide a polypropylene/polyamide/polyketone composition which has high hardness, excellent scratch resistance and good mechanical properties and can be applied to the fields of automobiles and household appliances such as automobile exterior decorations, air conditioner decorative strips and small household appliance exterior decorative structures.
The specific technical scheme is as follows:
the polypropylene/polyamide/polyketone composition is prepared from the following raw materials in parts by weight:
55-75 parts of polypropylene resin;
5-20 parts of polyamide resin;
10-30 parts of polyketone resin;
the sum of the parts by weight of the polypropylene resin, the polyamide resin and the polyketone resin is 100 parts;
the compatilizer is at least one of maleic anhydride grafted polypropylene and maleic anhydride grafted polyethylene;
the scratch-resistant agent consists of cubic boron nitride (c-BN) and hexagonal boron nitride (h-BN).
Preferably, the polypropylene/polyamide/polyketone composition is prepared from the following raw materials in parts by weight:
60-75 parts of polypropylene resin;
10-15 parts of polyamide resin;
15-25 parts of polyketone resin;
the sum of the parts by weight of the polypropylene resin, the polyamide resin and the polyketone resin is 100 parts;
preferably, the melt index of the polypropylene resin under the condition of 230 ℃/2.16kg is 10-30g/10 min; more preferably, the melt index of the polypropylene resin under the condition of 230 ℃/2.16kg is 15-25g/10 min; further preferably, the polypropylene resin has a melt index of 20g/10min at 230 ℃/2.16 kg.
Preferably, the polyamide resin is polyamide 6; the relative viscosity of the polyamide 6 is 2-5; more preferably, the relative viscosity of said polyamide 6 is between 2.5 and 3.5; further preferably, the relative viscosity of the polyamide 6 is 3.
Preferably, the melt index of the polyketone resin at 230 ℃/2.16kg is 1-20g/10 min; more preferably, the melt index of the polyketone resin at 230 ℃/2.16kg is 3-15g/10 min; further preferably, the melt index of the polyketone resin is 10g/10min at 230 ℃/2.16 kg.
Preferably, the scratch-resistant agent consists of cubic boron nitride and hexagonal boron nitride in a mass ratio of 1: 0.8-1.2.
Preferably, the cubic boron nitride has a particle size of 0.2 to 200 μm; more preferably, the cubic boron nitride has a particle size of 1 to 100 μm; further preferably, the cubic boron nitride has a particle size of 5 to 20 μm.
Preferably, the particle size of the hexagonal crystal boron nitride is 1-1000 μm; more preferably, the particle size of the hexagonal crystal boron nitride is 10-500 μm; further preferably, the particle size of the hexagonal crystal boron nitride is 50-200 μm.
Preferably, the antioxidant is at least one of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid N-octadecyl ester, tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and N, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) phosphite. The antioxidant improves the processing stability of matrix resin in the processing process of the polypropylene/polyamide/polyketone composition, and avoids the problems of material degradation and the like caused in the high-temperature processing process, thereby improving the overall performance of the material.
Preferably, the lubricant is at least one of silicone powder, calcium stearate and zinc stearate. The lubricant has good thermal stability and is not easy to decompose in the processing process of the polypropylene/polyamide/polyketone composition. Meanwhile, in order to improve the processability of the material and reduce the comprehensive energy consumption by considering the high viscosity of the polyamide resin in the formula, a lubricant is introduced, and the certain amount of the lubricant can obviously reduce the torque of the material in the processing process.
Another object of the present invention is to provide a process for the preparation of a polypropylene/polyamide/polyketone composition.
The specific technical scheme is as follows:
the preparation method of the polypropylene/polyamide/polyketone composition comprises the following steps:
mixing the polypropylene resin, the polyamide resin, the polyketone resin, the compatilizer, the scratch-resistant agent, the antioxidant and the lubricant, adding the obtained mixture into a parallel double-screw extruder for melt extrusion, and granulating to obtain the anti-scratch coating;
the technological parameters of the parallel double-screw extruder comprise: the temperature of the first zone is 150-170 ℃, the temperature of the second zone is 190-210 ℃, the temperature of the third zone is 190-210 ℃, the temperature of the fourth zone is 200-220 ℃, the temperature of the fifth zone is 200-220 ℃, the temperature of the sixth zone is 190-210 ℃, the temperature of the seventh zone is 210-230 ℃, the temperature of the eighth zone is 210-240 ℃, the temperature of the die head is 210-240 ℃, the rotating speed of the screw is 200-500 rpm, and the vacuum degree is-0.05-0.08 MPa.
Preferably, the process parameters of the parallel twin-screw extruder comprise: the temperature of the first zone is 160-170 ℃, the temperature of the second zone is 200-210 ℃, the temperature of the third zone is 200-210 ℃, the temperature of the fourth zone is 210-220 ℃, the temperature of the fifth zone is 210-220 ℃, the temperature of the sixth zone is 200-210 ℃, the temperature of the seventh zone is 220-230 ℃, the temperature of the eighth zone is 220-240 ℃, the temperature of the die head is 220-240 ℃, the rotating speed of the screw is 300-400 rpm, and the vacuum degree is-0.06-0.07 MPa.
Preferably, the ratio L/D of the length L and the diameter D of the screw of the parallel double-screw extruder is 35-50; the screw is provided with 1-2 meshing block areas and 1-2 reverse thread areas.
Preferably, the mixing is carried out in a high-speed stirrer, and the rotating speed of the high-speed stirrer is 500-1200 rpm; more preferably, the rotating speed of the high-speed stirrer is 700 and 1000 revolutions per minute.
The principle of the polypropylene-polyamide-polyketone composition of the invention is as follows:
according to the invention, polypropylene, polyamide and polyketone are used as matrix resin, hexagonal boron nitride and cubic boron nitride are used in a matching manner as a scratch-resistant agent, and a certain amount of specific compatilizer is matched to prepare the polymer composite material with high hardness, excellent wear resistance and excellent mechanical properties.
After a specific kind of compatilizer is introduced, one end of the compatilizer is a non-polar structure, the other end of the compatilizer is a polar structure, for example, maleic anhydride grafted polypropylene is taken as an example, one end of the compatilizer is polypropylene with a non-polar structure, the molecular structure of the compatilizer is similar to that of polypropylene, the compatilizer has good physical compatibility with polypropylene, and the other end of the compatilizer is maleic anhydride. In addition, due to the interaction of the molecules of the polyamide and the polyketone in the phase interface nanoscale, the two polymers can be physically blended to obtain good compatibility without any chemical reaction, so that the compatibility of the polypropylene, the polyketone and the polyamide can be greatly improved by adding the polyamide and matching with a proper amount of a specific kind of compatilizer, a polypropylene-nylon-polyketone three-component composition with better compatibility can be obtained, and the composition has excellent mechanical property and wear resistance. On the basis, the scratch-resistant agent cubic crystal boron nitride has very high hardness, so that the strength of a resin substrate can be further improved, and the wear resistance of the resin substrate is improved; the scratch-resistant agent hexagonal crystal boron nitride has a lamellar structure, can achieve a certain toughening effect while enhancing, has certain self-lubricating property, and can improve the scratch resistance of the material. The scratch-resistant agent has the advantages that the cubic boron nitride and the hexagonal boron nitride are used simultaneously, the obvious synergistic effect is achieved, three-component polymers of polypropylene, polyamide and polyketone are used as matrix resin, and the two boron nitride materials are matched, so that the hardness and the wear resistance of the material can be greatly improved, and the obtained material has excellent mechanical properties.
Therefore, the invention has the following beneficial effects:
the polypropylene/polyamide/polyketone composition has high hardness, excellent scratch resistance and wear resistance, and excellent mechanical property, can be applied to the kitchen electrical field such as the shell of an electric cooker and the shell of an electric pressure cooker, and can also be expanded to be used in the fields of automobile exterior decorations, air conditioner decorative strips, other small household appliances and the like.
The preparation method of the polypropylene/polyamide/polyketone composition provided by the invention has the advantages of simple preparation process, easiness in control and low requirement on equipment, all the used equipment are general processing equipment, the investment is low, and the preparation method is favorable for industrial production.
Drawings
FIG. 1 is a flow chart of a process for preparing a polypropylene-polyamide-polyketone composition according to an embodiment of the present invention;
FIG. 2 is a diagram of a practical article of the polypropylene-polyamide-polyketone composition of example 7 of the invention.
Detailed Description
In order that the invention may be more readily understood, reference will now be made to the following more particular description of the invention, examples of which are set forth below. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. These embodiments are provided so that this disclosure will be thorough and complete. It is to be understood that the experimental procedures in the following examples, where specific conditions are not noted, are generally in accordance with conventional conditions, or with conditions recommended by the manufacturer. The various reagents used in the examples are commercially available.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The raw material components and sources thereof used in the specific embodiment of the present invention are as follows:
polypropylene resin with a melt index of 20g/10min at 230 ℃/2.16kg, selected from China petrochemical group Michelson petrochemical company Limited;
polyamide 6 resin with relative viscosity of 3, selected from Henan Shenma Nylon chemical Limited liability company;
a polyketone resin having a melt index of 10g/10min selected from the group consisting of Xiaoxing, Korea;
a compatilizer: maleic anhydride grafted polypropylene selected from Shenyang Ketong, Inc.;
scratch-resistant agent: 10 μm cubic boron nitride selected from Shanghai Chaowei nanotechnology, Inc.;
scratch-resistant agent: 100 μm hexagonal boron nitride, available from Denton Rinji technology Ltd;
antioxidant: n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate and pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], selected from Beijing very easily available chemical Co., Ltd;
antioxidant: n, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) phosphite selected from Beijing Tiangang auxiliary agent, Limited liability company;
lubricant silicone powder selected from Sichuan polymerization Industrial technologies, Inc. of Guangzhou city;
lubricant calcium stearate, lubricant zinc stearate, selected from Zichuan Ruifeng plastics assistants;
the present invention will be described in detail with reference to specific examples.
Example 1
A polypropylene/polyamide/polyketone composition is prepared from the following raw materials in parts by weight:
the preparation method of the polypropylene/polyamide/polyketone composition comprises the following steps:
1) weighing the polypropylene resin, the polyamide resin, the polyketone resin, the scratch-resistant agent, the compatilizer, the antioxidant and the lubricant according to the parts by weight, and mixing by using a high-speed mixer at 500 revolutions per minute.
2) Adding the mixed material obtained in the step 1) into a parallel double-screw extruder through a main feeder, and performing melt extrusion and granulation, wherein the process parameters are as follows: the temperature of the first zone is 150 ℃, the temperature of the second zone is 190 ℃, the temperature of the third zone is 190 ℃, the temperature of the fourth zone is 200 ℃, the temperature of the fifth zone is 200 ℃, the temperature of the sixth zone is 190 ℃, the temperature of the seventh zone is 210 ℃, the temperature of the eighth zone is 210 ℃, the temperature of the die head is 210 ℃, the rotating speed of the screw is 200rpm, and the vacuum degree is-0.05 MPa; the ratio L/D of the length L of the screw to the diameter D is 35; and the screw is provided with 1 meshing block area and 1 reverse thread area.
And (3) carrying out melt extrusion and granulation by a double-screw extruder under the process conditions to obtain the granular polypropylene/polyamide/polyketone composition.
Example 2
A polypropylene/polyamide/polyketone composition is prepared from the following raw materials in parts by weight:
the preparation method of the polypropylene/polyamide/polyketone composition comprises the following steps:
1) weighing the polypropylene resin, the polyamide resin, the polyketone resin, the compatilizer, the scratch-resistant agent, the antioxidant and the lubricant according to the parts by weight, and mixing by using a high-speed stirrer at 800 revolutions per minute.
2) Adding the mixed material obtained in the step 1) into a parallel double-screw extruder through a main feeder for melt extrusion and granulation, wherein the process parameters are as follows: the temperature of the first zone is 160 ℃, the temperature of the second zone is 200 ℃, the temperature of the third zone is 200 ℃, the temperature of the fourth zone is 210 ℃, the temperature of the fifth zone is 210 ℃, the temperature of the sixth zone is 200 ℃, the temperature of the seventh zone is 230 ℃, the temperature of the eighth zone is 240 ℃, the temperature of the die head is 240 ℃, the rotating speed of the screw is 300rpm, and the vacuum degree is-0.06 MPa; the ratio L/D of the length L of the screw to the diameter D is 45; and the screw is provided with 1 meshing block area and 2 reverse thread areas.
And (3) carrying out melt extrusion and granulation by a double-screw extruder under the process conditions to obtain the granular polypropylene/polyamide/polyketone composition.
Example 3:
a polypropylene/polyamide/polyketone composition is prepared from the following raw materials in parts by weight:
the preparation method of the polypropylene/polyamide/polyketone composition comprises the following steps:
1) weighing the polypropylene resin, the polyamide resin, the polyketone resin, the compatilizer, the scratch-resistant agent, the antioxidant and the lubricant according to the parts by weight, and mixing by using a high-speed stirrer at 1200 rpm.
2) Adding the mixed material obtained in the step 1) into a parallel double-screw extruder through a main feeder for melt extrusion and granulation, wherein the process parameters are as follows: the temperature of the first zone is 170 ℃, the temperature of the second zone is 210 ℃, the temperature of the third zone is 210 ℃, the temperature of the fourth zone is 220 ℃, the temperature of the fifth zone is 220 ℃, the temperature of the sixth zone is 210 ℃, the temperature of the seventh zone is 210 ℃, the temperature of the eighth zone is 220 ℃, the temperature of the die head is 220 ℃, the rotating speed of the screw is 500rpm, and the vacuum degree is-0.08 MPa; the ratio L/D of the length L of the screw to the diameter D of the screw is 50; and the screw is provided with 2 meshing block areas and 2 reverse thread areas.
And carrying out melt extrusion and granulation by a double-screw extruder under the process conditions to obtain the polypropylene/polyamide/polyketone composition.
Example 4:
a polypropylene/polyamide/polyketone composition is prepared from the following raw materials in parts by weight:
the preparation method of the polypropylene/polyamide/polyketone composition comprises the following steps:
1) weighing the polypropylene resin, the polyamide resin, the polyketone resin, the compatilizer, the scratch-resistant agent, the antioxidant and the lubricant according to the parts by weight, and mixing by using a high-speed stirrer at 1200 rpm.
2) Adding the mixed material obtained in the step 1) into a parallel double-screw extruder through a main feeder, melting, extruding and granulating, wherein the process parameters are as follows: the temperature of the first zone is 170 ℃, the temperature of the second zone is 210 ℃, the temperature of the third zone is 210 ℃, the temperature of the fourth zone is 220 ℃, the temperature of the fifth zone is 220 ℃, the temperature of the sixth zone is 210 ℃, the temperature of the seventh zone is 210 ℃, the temperature of the eighth zone is 220 ℃, the temperature of the die head is 220 ℃, the rotating speed of the screw is 500rpm, and the vacuum degree is-0.08 MPa; the ratio L/D of the length L of the screw to the diameter D of the screw is 50; and the screw is provided with 2 meshing block areas and 2 reverse thread areas.
And carrying out melt extrusion and granulation by a double-screw extruder under the process conditions to obtain the polypropylene/polyamide/polyketone composition.
Example 5:
a polypropylene/polyamide/polyketone composition is prepared from the following raw materials in parts by weight:
the polypropylene/polyamide/polyketone composition and the preparation method thereof comprise the following steps:
1) weighing the polypropylene resin, the polyamide resin, the polyketone resin, the compatilizer, the scratch-resistant agent, the antioxidant and the lubricant according to the parts by weight, and mixing by using a high-speed stirrer at 1200 rpm.
2) Adding the mixed material obtained in the step 1) into a parallel double-screw extruder through a main feeder, melting, extruding and granulating, wherein the process parameters are as follows: the temperature of the first zone is 170 ℃, the temperature of the second zone is 210 ℃, the temperature of the third zone is 210 ℃, the temperature of the fourth zone is 220 ℃, the temperature of the fifth zone is 220 ℃, the temperature of the sixth zone is 210 ℃, the temperature of the seventh zone is 210 ℃, the temperature of the eighth zone is 220 ℃, the temperature of the die head is 220 ℃, the rotating speed of the screw is 500rpm, and the vacuum degree is-0.08 MPa; the ratio L/D of the length L of the screw to the diameter D of the screw is 50; and the screw is provided with 2 meshing block areas and 2 reverse thread areas.
And carrying out melt extrusion and granulation by a double-screw extruder under the process conditions to obtain the polypropylene/polyamide/polyketone composition.
Example 6:
a polypropylene/polyamide/polyketone composition is prepared from the following raw materials in parts by weight:
the polypropylene/polyamide/polyketone composition and the preparation method thereof comprise the following steps:
1) weighing the polypropylene resin, the polyamide resin, the polyketone resin, the compatilizer, the scratch-resistant agent, the antioxidant and the lubricant according to the parts by weight, and mixing by using a high-speed stirrer at 1200 rpm.
2) Adding the mixed material obtained in the step 1) into a parallel double-screw extruder through a main feeder, melting, extruding and granulating, wherein the process parameters are as follows: the temperature of the first zone is 170 ℃, the temperature of the second zone is 210 ℃, the temperature of the third zone is 210 ℃, the temperature of the fourth zone is 220 ℃, the temperature of the fifth zone is 220 ℃, the temperature of the sixth zone is 210 ℃, the temperature of the seventh zone is 210 ℃, the temperature of the eighth zone is 220 ℃, the temperature of the die head is 220 ℃, the rotating speed of the screw is 500rpm, and the vacuum degree is-0.08 MPa; the ratio L/D of the length L of the screw to the diameter D of the screw is 50; and the screw is provided with 2 meshing block areas and 2 reverse thread areas.
And carrying out melt extrusion and granulation by a double-screw extruder under the process conditions to obtain the polypropylene/polyamide/polyketone composition.
Example 7:
a polypropylene/polyamide/polyketone composition is prepared from the following raw materials in parts by weight:
the polypropylene/polyamide/polyketone composition and the preparation method thereof comprise the following steps:
1) weighing the polypropylene resin, the polyamide resin, the polyketone resin, the compatilizer, the scratch-resistant agent, the antioxidant and the lubricant according to the weight percentage, and mixing by using a high-speed stirrer at 1000 revolutions per minute.
2) Adding the mixed material obtained in the step 1) into a parallel double-screw extruder through a main feeder, melting, extruding and granulating, wherein the process parameters are as follows: the temperature of the first zone is 170 ℃, the temperature of the second zone is 210 ℃, the temperature of the third zone is 210 ℃, the temperature of the fourth zone is 220 ℃, the temperature of the fifth zone is 220 ℃, the temperature of the sixth zone is 210 ℃, the temperature of the seventh zone is 220 ℃, the temperature of the eighth zone is 220 ℃, the temperature of the die head is 220 ℃, the rotating speed of the screw is 350rpm, and the vacuum degree is-0.06 MPa; the ratio L/D of the length L of the screw to the diameter D of the screw is 50; and the screw is provided with 2 meshing block areas and 2 reverse thread areas.
And carrying out melt extrusion and granulation by a double-screw extruder under the process conditions to obtain the polypropylene/polyamide/polyketone composition.
The polypropylene/polyamide/polyketone composition obtained in this example was injection molded by a conventional method to obtain a product of the article shown in FIG. 2, and as can be seen from FIG. 2, the product had good scratch resistance.
Example 8:
a polypropylene/polyamide/polyketone composition is prepared from the following raw materials in parts by weight:
the polypropylene/polyamide/polyketone composition and the preparation method thereof comprise the following steps:
1) weighing the polypropylene resin, the polyamide resin, the polyketone resin, the compatilizer, the scratch-resistant agent, the antioxidant and the lubricant according to the weight percentage, and mixing by using a high-speed stirrer at 1000 revolutions per minute.
2) Adding the mixed material obtained in the step 1) into a parallel double-screw extruder through a main feeder, melting, extruding and granulating, wherein the process parameters are as follows: the temperature of the first zone is 170 ℃, the temperature of the second zone is 210 ℃, the temperature of the third zone is 210 ℃, the temperature of the fourth zone is 220 ℃, the temperature of the fifth zone is 220 ℃, the temperature of the sixth zone is 210 ℃, the temperature of the seventh zone is 220 ℃, the temperature of the eighth zone is 220 ℃, the temperature of the die head is 220 ℃, the rotating speed of the screw is 350rpm, and the vacuum degree is-0.06 MPa; the ratio L/D of the length L of the screw to the diameter D of the screw is 50; and the screw is provided with 2 meshing block areas and 2 reverse thread areas.
And carrying out melt extrusion and granulation by a double-screw extruder under the process conditions to obtain the polypropylene/polyamide/polyketone composition.
Comparative example 1:
a polypropylene/polyamide/polyketone composition is prepared from the following raw materials in parts by weight:
the polypropylene/polyamide/polyketone composition and the preparation method thereof comprise the following steps:
1) weighing the polypropylene resin, the polyamide resin, the polyketone resin, the compatilizer, the scratch-resistant agent, the antioxidant and the lubricant according to the parts by weight, and mixing by using a high-speed stirrer at 1200 rpm.
2) Adding the mixed material obtained in the step 1) into a parallel double-screw extruder through a main feeder, melting, extruding and granulating, wherein the process parameters are as follows: the temperature of the first zone is 170 ℃, the temperature of the second zone is 210 ℃, the temperature of the third zone is 210 ℃, the temperature of the fourth zone is 220 ℃, the temperature of the fifth zone is 220 ℃, the temperature of the sixth zone is 210 ℃, the temperature of the seventh zone is 210 ℃, the temperature of the eighth zone is 220 ℃, the temperature of the die head is 220 ℃, the rotating speed of the screw is 500rpm, and the vacuum degree is-0.08 MPa; the ratio L/D of the length L of the screw to the diameter D of the screw is 50; and the screw is provided with 2 meshing block areas and 2 reverse thread areas.
And carrying out melt extrusion and granulation by a double-screw extruder under the process conditions to obtain the polypropylene/polyamide/polyketone composition.
Comparative example 2:
a polypropylene/polyamide/polyketone composition is prepared from the following raw materials in parts by weight:
the polypropylene/polyamide/polyketone composition and the preparation method thereof comprise the following steps:
1) weighing the polypropylene resin, the polyamide resin, the polyketone resin, the compatilizer, the scratch-resistant agent, the antioxidant and the lubricant according to the parts by weight, and mixing by using a high-speed stirrer at 1200 rpm.
2) Adding the mixed material obtained in the step 1) into a parallel double-screw extruder through a main feeder, melting, extruding and granulating, wherein the process parameters are as follows: the temperature of the first zone is 170 ℃, the temperature of the second zone is 210 ℃, the temperature of the third zone is 210 ℃, the temperature of the fourth zone is 220 ℃, the temperature of the fifth zone is 220 ℃, the temperature of the sixth zone is 210 ℃, the temperature of the seventh zone is 210 ℃, the temperature of the eighth zone is 220 ℃, the temperature of the die head is 220 ℃, the rotating speed of the screw is 500rpm, and the vacuum degree is-0.08 MPa; the ratio L/D of the length L of the screw to the diameter D of the screw is 50; and the screw is provided with 2 meshing block areas and 2 reverse thread areas.
And carrying out melt extrusion and granulation by a double-screw extruder under the process conditions to obtain the polypropylene/polyamide/polyketone composition.
Comparative example 3:
a polypropylene/polyamide/polyketone composition is prepared from the following raw materials in parts by weight:
the polypropylene/polyamide/polyketone composition and the preparation method thereof comprise the following steps:
1) weighing the polypropylene resin, the polyamide resin, the polyketone resin, the compatilizer, the scratch-resistant agent, the antioxidant and the lubricant according to the parts by weight, and mixing by using a high-speed stirrer at 1200 rpm.
2) Adding the mixed material obtained in the step 1) into a parallel double-screw extruder through a main feeder, melting, extruding and granulating, wherein the process parameters are as follows: the temperature of the first zone is 170 ℃, the temperature of the second zone is 210 ℃, the temperature of the third zone is 210 ℃, the temperature of the fourth zone is 220 ℃, the temperature of the fifth zone is 220 ℃, the temperature of the sixth zone is 210 ℃, the temperature of the seventh zone is 210 ℃, the temperature of the eighth zone is 220 ℃, the temperature of the die head is 220 ℃, the rotating speed of the screw is 500rpm, and the vacuum degree is-0.08 MPa; the ratio L/D of the length L of the screw to the diameter D of the screw is 50; and the screw is provided with 2 meshing block areas and 2 reverse thread areas.
And carrying out melt extrusion and granulation by a double-screw extruder under the process conditions to obtain the polypropylene/polyamide/polyketone composition.
Comparative example 4:
a polypropylene/polyamide/polyketone composition is prepared from the following raw materials in parts by weight:
the polypropylene/polyamide/polyketone composition and the preparation method thereof comprise the following steps:
1) weighing the polypropylene resin, the polyamide resin, the polyketone resin, the compatilizer, the scratch-resistant agent, the antioxidant and the lubricant according to the parts by weight, and mixing by using a high-speed stirrer at 1200 rpm.
2) Adding the mixed material obtained in the step 1) into a parallel double-screw extruder through a main feeder, wherein the temperature of a middle zone is 210 ℃, the temperature of a fourth zone is 220 ℃, the temperature of a fifth zone is 220 ℃, the temperature of a sixth zone is 210 ℃, the temperature of a seventh zone is 210 ℃, the temperature of an eighth zone is 220 ℃, the temperature of a die head is 220 ℃, the rotating speed of a screw is 500rpm, and the vacuum degree is-0.08 MPa; the ratio L/D of the length L of the screw to the diameter D of the screw is 50; and the screw is provided with 2 meshing block areas and 2 reverse thread areas.
And carrying out melt extrusion and granulation by a double-screw extruder under the process conditions to obtain the polypropylene/polyamide/polyketone composition.
Comparative example 5:
a polypropylene/polyamide/polyketone composition is prepared from the following raw materials in parts by weight:
the polypropylene/polyamide/polyketone composition and the preparation method thereof comprise the following steps:
1) weighing the polypropylene resin, the polyamide resin, the polyketone resin, the compatilizer, the scratch-resistant agent, the antioxidant and the lubricant according to the parts by weight, and mixing by using a high-speed stirrer at 1200 rpm.
2) Adding the mixed material obtained in the step 1) into a parallel double-screw extruder through a main feeder, melting, extruding and granulating, wherein the process parameters are as follows: the temperature of the first zone is 170 ℃, the temperature of the second zone is 210 ℃, the temperature of the third zone is 210 ℃, the temperature of the fourth zone is 220 ℃, the temperature of the fifth zone is 220 ℃, the temperature of the sixth zone is 210 ℃, the temperature of the seventh zone is 210 ℃, the temperature of the eighth zone is 220 ℃, the temperature of the die head is 220 ℃, the rotating speed of the screw is 500rpm, and the vacuum degree is-0.08 MPa; the ratio L/D of the length L of the screw to the diameter D of the screw is 50; and the screw is provided with 2 meshing block areas and 2 reverse thread areas.
And carrying out melt extrusion and granulation by a double-screw extruder under the process conditions to obtain the polypropylene/polyamide/polyketone composition.
Comparative example 6:
a polypropylene/polyamide/polyketone composition is prepared from the following raw materials in parts by weight:
the polypropylene/polyamide/polyketone composition and the preparation method thereof comprise the following steps:
1) weighing the polypropylene resin, the polyamide resin, the polyketone resin, the compatilizer, the scratch-resistant agent, the antioxidant and the lubricant according to the parts by weight, and mixing by using a high-speed stirrer at 1200 rpm.
2) Adding the mixed material obtained in the step 1) into a parallel double-screw extruder through a main feeder, melting, extruding and granulating, wherein the process parameters are as follows: the temperature of the first zone is 170 ℃, the temperature of the second zone is 210 ℃, the temperature of the third zone is 210 ℃, the temperature of the fourth zone is 220 ℃, the temperature of the fifth zone is 220 ℃, the temperature of the sixth zone is 210 ℃, the temperature of the seventh zone is 210 ℃, the temperature of the eighth zone is 220 ℃, the temperature of the die head is 220 ℃, the rotating speed of the screw is 500rpm, and the vacuum degree is-0.08 MPa; the ratio L/D of the length L of the screw to the diameter D of the screw is 50; and the screw is provided with 2 meshing block areas and 2 reverse thread areas.
And carrying out melt extrusion and granulation by a double-screw extruder under the process conditions to obtain the polypropylene/polyamide/polyketone composition.
Comparative example 7:
a polypropylene/polyamide/polyketone composition is prepared from the following raw materials in parts by weight:
the polypropylene/polyamide/polyketone composition and the preparation method thereof comprise the following steps:
1) weighing the polypropylene resin, the polyamide resin, the polyketone resin, the compatilizer, the scratch-resistant agent, the antioxidant and the lubricant according to the weight percentage, and mixing by using a high-speed stirrer at 1000 revolutions per minute.
2) Adding the mixed material obtained in the step 1) into a parallel double-screw extruder through a main feeder, melting, extruding and granulating, wherein the process parameters are as follows: the temperature of the first zone is 170 ℃, the temperature of the second zone is 210 ℃, the temperature of the third zone is 210 ℃, the temperature of the fourth zone is 220 ℃, the temperature of the fifth zone is 220 ℃, the temperature of the sixth zone is 210 ℃, the temperature of the seventh zone is 220 ℃, the temperature of the eighth zone is 220 ℃, the temperature of the die head is 220 ℃, the rotating speed of the screw is 350rpm, and the vacuum degree is-0.06 MPa; the ratio L/D of the length L of the screw to the diameter D of the screw is 50; and the screw is provided with 2 meshing block areas and 2 reverse thread areas.
And carrying out melt extrusion and granulation by a double-screw extruder under the process conditions to obtain the polypropylene/polyamide/polyketone composition.
The following is a list of raw material compositions of examples and comparative examples (table 1).
TABLE 1 summary of the composition parts by weight of the raw materials of the examples and comparative examples
The polypropylene/polyamide/polyketone compositions prepared in the above examples and comparative examples were subjected to the following performance tests:
tensile property: testing according to GB/T1040-2006 standard, wherein the stretching speed is 50 mm/min;
bending property: according to the test of GB/T9341-;
rockwell hardness: testing according to GB/T230.1-2009 standard;
scratch resistance: according to the GMW 14688-.
The results of the performance tests are shown in table 2.
TABLE 2 Properties of the Polypropylene/Polyamide/polyketone compositions of the examples and comparative examples
In examples 1 to 7, the proportions of the polypropylene resin, the polyamide resin, the polyketone resin, the scratch-resistant agent, the compatibilizer, the antioxidant and the lubricant were adjusted, and it can be seen from the table that, when the content of the polypropylene resin is decreased (the content of the polyamide resin and the content of the polyketone resin are increased) within a certain range, the tensile strength, the flexural strength, the hardness and the scratch resistance of the polypropylene/polyamide/polyketone composition are slightly increased. Within a certain range, the increase or decrease of the compatilizer has little influence on the mechanical property of the system, and the content change of the antioxidant and the lubricant has little influence on the mechanical property of the system. As the addition amount of the scratch resistant agent is increased, the hardness and the scratch resistance of the polypropylene/polyamide/polyketone composition are obviously improved, but the hardness and the scratch resistance are improved at an upper limit, and after the addition amount reaches a certain value (such as 4 parts in example 7), the content of cubic boron nitride and hexagonal boron nitride is further increased, so that the overall performance of the polypropylene/polyamide/polyketone composition is not obviously influenced. By comparison, the overall performance of example 7 is best.
Comparative examples 1 and 2 compared to example 7, comparative examples 1 and 2 used less polyamide and polyketone resin, respectively, and the resulting polypropylene/polyamide/polyketone compositions all had a significant decrease in tensile strength, flexural strength, hardness, and scratch resistance; comparative example 3 compared with example 7, the polypropylene/polyamide/polyketone composition obtained by using too little compatilizer in comparative example 3 has obviously reduced overall mechanical properties, because the polypropylene/polyamide/polyketone composition has obvious phase separation due to too little compatilizer, the material is easy to generate defects at the edges of the phase, and the defects are easy to convert into cracks under stress, so that the material has reduced properties. Comparative examples 4 and 5 compared to example 7, comparative examples 4 and 5, respectively, used only one scratch resistant agent, and resulted in polypropylene/polyamide/polyketone compositions having a significant reduction in both hardness and scratch resistance. Comparative example 6 is the worst in hardness and scratch resistance compared to example 7 because a scratch resistant agent was not added. The fact shows that the combination of the three resin matrixes and the compounding of the scratch-resistant agent can greatly influence the hardness and the scratch-resistant effect of the finally obtained composite material, and the composite material with better performance can be obtained only by combining the components. Comparative example 7 has a significantly reduced content of polypropylene compared to example 7, resulting in a significant deterioration of the mechanical properties of the resulting polypropylene/polyamide/polyketone composition, mainly due to the transformation of the matrix of the ternary blend system, increasing the content of polyamide and polyketone in turn resulting in problems of compatibility between the resins, further resulting in a significant reduction of the overall mechanical properties of the polypropylene/polyamide/polyketone composition.
The technical features of the above embodiments can be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the above embodiments are not described, however, as long as there is no contradiction between the combinations of the technical features, the scope of the present description should be considered as being described in the present specification.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The polypropylene/polyamide/polyketone composition is characterized by being prepared from the following raw materials in parts by weight:
55-75 parts of polypropylene resin;
5-20 parts of polyamide resin;
10-30 parts of polyketone resin;
the sum of the parts by weight of the polypropylene resin, the polyamide resin and the polyketone resin is 100 parts;
the compatilizer is at least one of maleic anhydride grafted polypropylene and maleic anhydride grafted polyethylene;
the scratch-resistant agent consists of cubic boron nitride and hexagonal boron nitride.
2. The polypropylene/polyamide/polyketone composition according to claim 1, which is prepared from the following raw materials in parts by weight:
60-75 parts of polypropylene resin;
10-15 parts of polyamide resin;
15-25 parts of polyketone resin;
the sum of the parts by weight of the polypropylene resin, the polyamide resin and the polyketone resin is 100 parts;
3. the polypropylene/polyamide/polyketone composition according to claim 1, wherein said polypropylene resin has a melt index of 10 to 30g/10min at 230 ℃/2.16 kg; and/or the presence of a catalyst in the reaction mixture,
the polyamide resin is polyamide 6; the relative viscosity of the polyamide 6 is 2-5; and/or the presence of a catalyst in the reaction mixture,
the melt index of the polyketone resin under the condition of 230 ℃/2.16kg is 1-20g/10 min.
4. The polypropylene/polyamide/polyketone composition according to claim 3, wherein said polypropylene resin has a melt index of 15 to 25g/10min at 230 ℃/2.16 kg; and/or the presence of a catalyst in the reaction mixture,
the relative viscosity of the polyamide 6 is 2.5-3.5; and/or the presence of a catalyst in the reaction mixture,
the melt index of the polyketone resin under the condition of 230 ℃/2.16kg is 3-15g/10 min.
5. The polypropylene/polyamide/polyketone composition according to claim 1, wherein the scratch resistant agent consists of cubic boron nitride and hexagonal boron nitride in a mass ratio of 1: 0.8-1.2.
6. The polypropylene/polyamide/polyketone composition according to any of claims 1 to 5, wherein the cubic boron nitride has a particle size of 0.2 to 200 μm; and/or the presence of a catalyst in the reaction mixture,
the grain diameter of the hexagonal crystal boron nitride is 1-1000 mu m.
7. The polypropylene/polyamide/polyketone composition according to claim 6, wherein the cubic boron nitride has a particle size of 1-100 μm; and/or the presence of a catalyst in the reaction mixture,
the grain diameter of the hexagonal crystal boron nitride is 50-200 μm.
8. The polypropylene/polyamide/polyketone composition according to any of claims 1 to 5, wherein the antioxidant is at least one of N-octadecyl β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) phosphite; and/or the presence of a catalyst in the reaction mixture,
the lubricant is at least one of silicone powder, calcium stearate and zinc stearate.
9. Process for the preparation of a polypropylene/polyamide/polyketone composition according to any one of claims 1 to 8, characterized in that it comprises the following steps:
mixing the polypropylene resin, the polyamide resin, the polyketone resin, the compatilizer, the scratch-resistant agent, the antioxidant and the lubricant, adding the obtained mixture into a parallel double-screw extruder for melt extrusion, and granulating to obtain the anti-scratch coating;
the technological parameters of the parallel double-screw extruder comprise: the temperature of the first zone is 150-170 ℃, the temperature of the second zone is 190-210 ℃, the temperature of the third zone is 190-210 ℃, the temperature of the fourth zone is 200-220 ℃, the temperature of the fifth zone is 200-220 ℃, the temperature of the sixth zone is 190-210 ℃, the temperature of the seventh zone is 210-230 ℃, the temperature of the eighth zone is 210-240 ℃, the temperature of the die head is 210-240 ℃, the rotating speed of the screw is 200-500 rpm, and the vacuum degree is-0.05-0.08 MPa.
10. The process for the preparation of a polypropylene/polyamide/polyketone composition according to claim 9, wherein the process parameters of the parallel twin-screw extruder comprise: the temperature of the first zone is 160-170 ℃, the temperature of the second zone is 200-210 ℃, the temperature of the third zone is 200-210 ℃, the temperature of the fourth zone is 210-220 ℃, the temperature of the fifth zone is 210-220 ℃, the temperature of the sixth zone is 200-210 ℃, the temperature of the seventh zone is 220-230 ℃, the temperature of the eighth zone is 220-240 ℃, the temperature of the die head is 220-240 ℃, the rotating speed of the screw is 300-400 rpm, and the vacuum degree is-0.06-0.07 MPa; and/or the presence of a catalyst in the reaction mixture,
the ratio L/D of the length L and the diameter D of the screw of the parallel double-screw extruder is 35-50; the screw is provided with 1-2 meshing block areas and 1-2 reverse thread areas.
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