CN116144102B - High-toughness polypropylene material and preparation method thereof - Google Patents
High-toughness polypropylene material and preparation method thereof Download PDFInfo
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- CN116144102B CN116144102B CN202111410201.5A CN202111410201A CN116144102B CN 116144102 B CN116144102 B CN 116144102B CN 202111410201 A CN202111410201 A CN 202111410201A CN 116144102 B CN116144102 B CN 116144102B
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- -1 polypropylene Polymers 0.000 title claims abstract 30
- 239000004743 Polypropylene Substances 0.000 title claims abstract 27
- 229920001155 polypropylene Polymers 0.000 title claims abstract 27
- 239000000463 material Substances 0.000 title claims abstract 26
- 238000002360 preparation method Methods 0.000 title claims abstract 3
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract 29
- 150000004706 metal oxides Chemical class 0.000 claims abstract 29
- 239000003963 antioxidant agent Substances 0.000 claims abstract 9
- 230000003078 antioxidant effect Effects 0.000 claims abstract 7
- 239000012745 toughening agent Substances 0.000 claims abstract 5
- 239000011248 coating agent Substances 0.000 claims abstract 2
- 238000000576 coating method Methods 0.000 claims abstract 2
- 239000002994 raw material Substances 0.000 claims abstract 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 6
- 238000001035 drying Methods 0.000 claims 5
- 229910052751 metal Inorganic materials 0.000 claims 5
- 239000002184 metal Substances 0.000 claims 5
- 238000003756 stirring Methods 0.000 claims 5
- 239000007864 aqueous solution Substances 0.000 claims 4
- 239000000843 powder Substances 0.000 claims 4
- 150000003839 salts Chemical class 0.000 claims 4
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims 3
- 239000002243 precursor Substances 0.000 claims 3
- 239000003381 stabilizer Substances 0.000 claims 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims 2
- GVHCUJZTWMCYJM-UHFFFAOYSA-N chromium(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GVHCUJZTWMCYJM-UHFFFAOYSA-N 0.000 claims 2
- 229910052802 copper Inorganic materials 0.000 claims 2
- 239000010949 copper Substances 0.000 claims 2
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 claims 2
- 238000010438 heat treatment Methods 0.000 claims 2
- 238000000034 method Methods 0.000 claims 2
- 238000002156 mixing Methods 0.000 claims 2
- 239000002245 particle Substances 0.000 claims 2
- 239000002530 phenolic antioxidant Substances 0.000 claims 2
- 229910052684 Cerium Inorganic materials 0.000 claims 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical group CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims 1
- 229910052793 cadmium Inorganic materials 0.000 claims 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 1
- 229910052804 chromium Inorganic materials 0.000 claims 1
- 239000011651 chromium Substances 0.000 claims 1
- 229910017052 cobalt Inorganic materials 0.000 claims 1
- 239000010941 cobalt Substances 0.000 claims 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims 1
- 238000001816 cooling Methods 0.000 claims 1
- 238000002425 crystallisation Methods 0.000 claims 1
- 230000008025 crystallization Effects 0.000 claims 1
- 238000004090 dissolution Methods 0.000 claims 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims 1
- 238000001125 extrusion Methods 0.000 claims 1
- 238000011049 filling Methods 0.000 claims 1
- 238000001914 filtration Methods 0.000 claims 1
- 229910052733 gallium Inorganic materials 0.000 claims 1
- 239000000499 gel Substances 0.000 claims 1
- 125000003827 glycol group Chemical group 0.000 claims 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 238000000227 grinding Methods 0.000 claims 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- 229910052742 iron Inorganic materials 0.000 claims 1
- HEQBUZNAOJCRSL-UHFFFAOYSA-N iron(ii) chromite Chemical compound [O-2].[O-2].[O-2].[Cr+3].[Fe+3] HEQBUZNAOJCRSL-UHFFFAOYSA-N 0.000 claims 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims 1
- 239000011259 mixed solution Substances 0.000 claims 1
- 229910052758 niobium Inorganic materials 0.000 claims 1
- 239000010955 niobium Substances 0.000 claims 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims 1
- 229910052709 silver Inorganic materials 0.000 claims 1
- 239000004332 silver Substances 0.000 claims 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 239000010936 titanium Substances 0.000 claims 1
- 229910052719 titanium Inorganic materials 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 239000011240 wet gel Substances 0.000 claims 1
- 229910052725 zinc Inorganic materials 0.000 claims 1
- 239000011701 zinc Substances 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract 2
- 238000000465 moulding Methods 0.000 abstract 1
- 231100000252 nontoxic Toxicity 0.000 abstract 1
- 230000003000 nontoxic effect Effects 0.000 abstract 1
Classifications
-
- 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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- 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)
Abstract
The invention discloses a high-toughness polypropylene material and a preparation method thereof. The polypropylene material is prepared from the following raw materials in percentage by weight: 0-6% of toughening agent, 3-8% of hollow metal oxide, 0-2% of antioxidant and 100% of polypropylene; the hollow metal oxide is obtained by coating the surface of POSS with metal oxide. The polypropylene material of the invention can be used for laser direct molding technology, has good heat resistance and excellent mechanical property, and is environment-friendly, nontoxic, low in price and simple in processing technology.
Description
Technical Field
The invention relates to the field of materials, in particular to a high-toughness polypropylene material for laser forming and a preparation method thereof.
Background
The three-dimensional molded interconnection device (3D-MID) is also called as a three-dimensional circuit or a three-dimensional circuit, and is characterized in that wires and patterns with electric functions are manufactured on an injection molded plastic shell, so that the functions of the electric interconnection function, the supporting component function, the supporting and protecting functions of the plastic shell and the like of a common circuit board are integrated into a whole, and a three-dimensional circuit carrier, namely the three-dimensional molded interconnection device, is formed. The three-dimensional molded interconnection device has the design advantages of being capable of selecting a shape, new in function and suitable for smaller and lighter development trends according to design requirements, and has the advantages of reducing installation levels, reducing the number of components, improving reliability, reducing the investment of the number and variety of materials, being beneficial to environmental protection treatment and the like. The 3D-MID has a considerable number of applications in the fields of automobiles, industry, computers, communication and the like, and is an important branch of the circuit board industry.
The 3D-MID mainly comprises two modes of 2ShotMID (double-mode injection molding) and LASER DIRECT Structure MID (LDS MID for short), and is mainly applied to LDS at present. LDS is the English abbreviation of Laser-Direct-Structuring, which means that a computer is used to control the movement of Laser according to the track of a conductive pattern, the Laser is irradiated onto a molded three-dimensional plastic device, and a circuit pattern is activated within a few seconds.
The plastics for laser direct structuring disclosed in CN101784607A, CN102066473A, CN102066122a and the like are all added with a non-conductive organometallic compound (such as copper salt or copper chromium) with spinel structure as an LDS additive, and the organometallic compound is expensive and is unfavorable for popularization and use of the plastics for laser direct structuring.
Patent CN109694572a discloses a polyamide composition comprising polyamide and hollow metal oxide particles, a process for its preparation and its use; the hollow metal oxide particles comprise hollow microspheres and metal oxides coated on the surfaces of the hollow microspheres, wherein the metal oxides can be activated by laser to form metal cores. The polyamide composition is prepared by melt-extruding polyamide and hollow metal oxide particles by an extruder. However, when the hollow metal oxide is synthesized, high-temperature calcination is needed, and agglomeration of powder is easily caused, so that the dispersibility of the product is poor, and the quality stability of the product and the binding force of a metal coating are finally affected.
Disclosure of Invention
Based on the above, the invention aims to provide a polypropylene material which is low in price, good in mechanical property and capable of being directly molded by laser.
The specific technical scheme is as follows:
the high-toughness polypropylene material is prepared from the following raw materials in percentage by weight:
the hollow metal oxide is obtained by coating the surface of POSS with metal oxide.
In some of these embodiments, the hollow metal oxide is 3-7% by weight.
In some of these embodiments, the hollow metal oxide is 3-6% by weight.
In some of these embodiments, the hollow metal oxide is 3-5% by weight.
In some of these embodiments, the hollow metal oxide is 3.5-4.5% by weight.
In some of these embodiments, the hollow metal oxide is 4% by weight.
In some of these embodiments, the weight percentage of the metal oxide in the hollow metal oxide is 35-70%.
In some of these embodiments, the weight percentage of the metal oxide in the hollow metal oxide is 45-65%.
In some of these embodiments, the weight percentage of the metal oxide in the hollow metal oxide is 50-60%.
In some of these embodiments, the metal element in the metal oxide is one or more of copper, silver, gold, zinc, cadmium, gallium, titanium, chromium, cobalt, manganese, cerium, niobium, and iron.
In some of these embodiments, the metal oxide is copper chrome black.
In some of these embodiments, the hollow metal oxide has a density of 1g/cm 3-6g/cm3.
In some of these embodiments, the hollow metal oxide has a density of 1.2g/cm 3-4g/cm3.
In some of these embodiments, the hollow metal oxide has a density of 1.5g/cm 3-2.7g/cm3.
In some of these embodiments, the hollow metal oxide has a particle size of 0.1 μm to 100 μm.
In some of these embodiments, the hollow metal oxide has a particle size of 0.5 μm to 50 μm.
In some embodiments, the hollow metal oxide is prepared from a metal salt corresponding to the metal oxide and an aminophenyl POSS by a sol-gel process or a hydrothermal process.
In some of these embodiments, the metal oxide corresponds to a mass ratio of metal salt to amine phenyl POSS of 1-5:1.
In some of these embodiments, the metal oxide corresponds to a mass ratio of metal salt to amine phenyl POSS of 3-4:1.
In some of these embodiments, the metal salts corresponding to the metal oxides are copper nitrate trihydrate and chromium nitrate nonahydrate.
In some of these embodiments, the mass ratio of copper nitrate trihydrate to chromium nitrate nonahydrate is from 1:1.5 to 2.5.
In some of these embodiments, the method of preparing the hollow metal oxide includes the steps of:
(1) Mixing the aminophenyl POSS and the metal salt corresponding to the metal oxide, and adding water for dissolution;
(2) Heating the mixed solution prepared in the step (1), dropwise adding a citric acid aqueous solution under stirring, adding a sol stabilizer after the dropwise adding is finished, continuing stirring until the sol is converted into gel, and stopping stirring;
(3) Drying the wet gel prepared in the step (2), and grinding into powder to obtain precursor powder;
(4) And adding water into the precursor powder for crystallization to obtain the hollow metal oxide.
In some of these embodiments, the ratio of the total mass of the aminophenyl POSS and the metal salt to water in step (1) is 1g:4mL-8mL.
In some of these embodiments, the heating temperature of step (2) is from 70 ℃ to 90 ℃.
In some embodiments, the stirring in step (2) is performed at a speed of 1000r/min to 1400r/min.
In some embodiments, the stirring in step (2) is performed at a speed of 1100r/min to 1300r/min.
In some embodiments, the concentration of the aqueous solution of citric acid is 0.07g/mL-0.10g/mL, and the amount of the aqueous solution of citric acid added dropwise is the same as the amount of water added in step (1).
In some of these embodiments, the sol stabilizer is ethylene glycol added in an amount of 0.1% -0.3% of the total volume of the aqueous citric acid solution and the water in step (1).
In some embodiments, the drying in the step (3) is constant temperature drying under the conditions that the vacuum degree is-0.5 Mpa to-0.7 Mpa and the temperature is 70 ℃ to 90 ℃.
In some of these embodiments, step (4) comprises: and (3) filling the precursor powder into a reaction kettle, adding water, uniformly stirring, screwing a kettle cover, crystallizing for 2-7 days under the conditions of the pressure of 15-20 MPa and the temperature of 280-320 ℃, filtering, washing and drying the product to obtain the hollow metal oxide.
In some embodiments, the drying conditions in step (4) include: the temperature is 90-110 ℃ and the time is 6-10 hours.
In some of these embodiments, the toughening agent is present in an amount of 2 to 5 weight percent.
In some embodiments, the antioxidant is present in an amount of 0.2 to 0.5 weight percent.
In some of these embodiments, the toughening agent is POE.
In some of these embodiments, the antioxidant consists of a hindered phenolic antioxidant and a phosphite antioxidant.
In some of these embodiments, the hindered phenolic antioxidant and the phosphite antioxidant are the same weight percent.
In some of these embodiments, the hindered phenolic antioxidant is stearyl β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate; the phosphite antioxidant is tris (2, 4-di-tert-butylphenyl) phosphite.
The invention also aims to provide a preparation method of the high-toughness polypropylene material.
The specific technical scheme is as follows:
The preparation method of the high-toughness polypropylene material comprises the following steps:
(a) Mixing the polypropylene with the toughening agent and the antioxidant after drying to obtain a premix;
(b) Adding the premix obtained in the step (a) into a parallel double-screw extruder through a main feeder, adding the hollow metal oxide in the lateral direction of the parallel double-screw extruder, and carrying out melt extrusion;
(c) And (c) bracing, cooling and granulating the extruded material obtained in the step (b) to obtain the high-toughness polypropylene material.
In some of these embodiments, the drying conditions of step (a) comprise: the temperature is 80-90 ℃ and the time is 3-5 h.
In some of these embodiments, the processing conditions of the parallel twin screw extruder include: the temperature of the first area is 180-200 ℃, the temperature of the second area is 200-225 ℃, the temperature of the third area is 220-235 ℃, the temperature of the fourth area is 220-235 ℃, the temperature of the fifth area is 220-235 ℃, the temperature of the sixth area is 220-235 ℃, the temperature of the seventh area is 220-235 ℃, the temperature of the eighth area is 220-235 ℃, the temperature of the ninth area is 210-225 ℃, the temperature of the die head is 220-235 ℃, and the residence time of the materials in the charging barrel of the parallel double-screw extruder is controlled to be 1-3 minutes.
The invention prepares the hollow metal oxide coated on the surface of the POSS by the metal oxide, and discovers that the hollow metal oxide coated on the surface of the POSS by the metal oxide is added into the polypropylene material to be used as an LDS additive, so that the obtained polypropylene material can be used for laser direct molding and has good bonding force with a metal coating. Compared with the material directly taking metal oxide as the LDS additive, the LDS additive added by the polypropylene composition provided by the invention is less, the metal coating adhesive force after laser etching is higher, the mechanical property is better, the cost is lower, when the addition amount of the hollow metal oxide particles is 3wt%, the metal coating adhesive force can reach the requirement, and when the addition amount of the hollow metal oxide particles is 4wt%, the metal coating adhesive force can reach the 5B grade; and has the advantages of environmental protection, no toxicity, low price, simple processing technique and the like.
In addition, the hollow metal oxide of the invention is matched with a toughening agent (preferably POE) with a certain dosage, so that the notch impact strength of the obtained polypropylene material can be further improved, and the toughness of the polypropylene material is improved, thereby obtaining more excellent mechanical properties while having excellent metal coating adhesive force.
Detailed Description
The technical scheme of the invention is further described by the following specific examples. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
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.
The terms "comprising" and "having" and any variations thereof, are intended to cover a non-exclusive inclusion. For example, a process, method, apparatus, article, or device that comprises a list of steps is not limited to the elements or modules listed but may alternatively include additional steps not listed or inherent to such process, method, article, or device.
In the present invention, the term "plurality" means two or more. "and/or", describes an association relationship of an association object, and indicates that there may be three relationships, for example, a and/or B, and may indicate: a exists alone, A and B exist together, and B exists alone. The character "/" generally indicates that the context-dependent object is an "or" relationship.
The raw materials used in the examples and comparative examples of the present invention are as follows:
polypropylene, table plastic, brand 1120;
Toughening agent POE, mitsui chemistry, brand A-1050S;
amine phenyl POSS, shanghai vast chemical industry limited;
copper nitrate trihydrate, san-foreign chemical trade company, tianjin;
Chromium nitrate nonahydrate, division of kepler biotechnology, shandong;
Citric acid monohydrate, kepler biotechnology limited, shandong;
ethylene glycol, tabacco Hengxin chemical technology Co., ltd;
Copper chrome black, polymaleic acid 42-303B.
The following are specific examples.
The copper chromium black content in the hollow copper chromium black particles in the following examples was calculated by the following method: firstly, measuring the content of copper and chromium in the obtained hollow copper-chromium black particles, then calculating the quality of the corresponding copper-chromium black according to the content of copper and chromium and the molecular formula CuCr 2O4 of the copper-chromium black, and dividing the quality of the copper-chromium black by the quality of the obtained hollow copper-chromium black particles to obtain the content of copper-chromium black in the hollow copper-chromium black particles.
EXAMPLE 1 preparation of hollow copper chromium Black particles
20G of aminophenyl POSS, 20g of copper nitrate trihydrate, 40g of chromium nitrate nonahydrate were mixed, added with 500ml of distilled water to be sufficiently dissolved, and transferred into a flask; 45g of citric acid monohydrate was weighed and formulated into 500mL of an aqueous solution of citric acid; placing the flask in a constant-temperature water bath kettle, setting a stirring device, stirring the mixture at the water bath temperature of 80 ℃ under strong stirring (the rotating speed of 1200 r/min), slowly dripping the aqueous solution of citric acid into the flask through a dropping funnel, and adding 2ml of glycol for stabilizing sol after the dripping is completed; continuously stirring until the sol is converted into gel, stopping stirring, placing the obtained wet gel in a vacuum drying oven with the vacuum degree of-0.6 Mpa, drying at the constant temperature of 80 ℃ to obtain xerogel, and grinding the obtained xerogel into powder to obtain precursor powder; then the precursor powder is put into a stainless steel reaction kettle with a polytetrafluoroethylene lining, deionized water is added, after uniform stirring, the kettle cover is screwed, the pressure is set to 18MPa, and crystallization is carried out for 5 days at 300 ℃. The obtained product is filtered, washed and dried in air at 100 ℃ for 8 hours, thus obtaining the hollow copper-chromium black particles, wherein the copper-chromium black content is 50wt%, the particle size is 0.5-50 mu m, and the density is 1.9g/cm 3.
Preparation example 2 preparation of hollow copper chromium black particles
15G of aminophenyl POSS, 20g of copper nitrate trihydrate, 40g of chromium nitrate nonahydrate were mixed, added with 500ml of distilled water to make them sufficiently dissolved, and transferred into a flask; 45g of citric acid monohydrate was weighed and formulated into 500mL of an aqueous solution of citric acid; placing the flask in a constant-temperature water bath kettle, setting a stirring device, stirring the mixture at the water bath temperature of 80 ℃ under strong stirring (the rotating speed of 1200 r/min), slowly dripping the aqueous solution of citric acid into the flask through a dropping funnel, and adding 2ml of glycol for stabilizing sol after the dripping is completed; continuously stirring until the sol is converted into gel, stopping stirring, placing the obtained wet gel in a vacuum drying oven with the vacuum degree of-0.6 Mpa, drying at the constant temperature of 80 ℃ to obtain xerogel, and grinding the obtained xerogel into powder to obtain precursor powder; then the precursor powder is put into a stainless steel reaction kettle with a polytetrafluoroethylene lining, deionized water is added, after uniform stirring, the kettle cover is screwed, the pressure is set to 18MPa, and crystallization is carried out for 5 days at 300 ℃. The obtained product is filtered, washed and dried in air at 100 ℃ for 8 hours, thus obtaining the hollow copper-chromium black particles, wherein the copper-chromium black content is 60wt%, the particle size is 0.5-50 mu m, and the density is 2.2g/cm 3.
Preparation example 3 preparation of hollow copper chromium black particles
40G of aminophenyl POSS, 20g of copper nitrate trihydrate, 40g of chromium nitrate nonahydrate were mixed, added with 500ml of distilled water to make them fully dissolved, and transferred into a flask; 45g of citric acid monohydrate was weighed and formulated into 500mL of an aqueous solution of citric acid; placing the flask in a constant-temperature water bath kettle, setting a stirring device, stirring the mixture at the water bath temperature of 80 ℃ under strong stirring (the rotating speed of 1200 r/min), slowly dripping the aqueous solution of citric acid into the flask through a dropping funnel, and adding 2ml of glycol for stabilizing sol after the dripping is completed; continuously stirring until the sol is converted into gel, stopping stirring, placing the obtained wet gel in a vacuum drying oven with the vacuum degree of-0.6 Mpa, drying at the constant temperature of 80 ℃ to obtain xerogel, and grinding the obtained xerogel into powder to obtain precursor powder; then the precursor powder is put into a stainless steel reaction kettle with a polytetrafluoroethylene lining, deionized water is added, after uniform stirring, the kettle cover is screwed, the pressure is set to 18MPa, and crystallization is carried out for 5 days at 300 ℃. The obtained product is filtered, washed and dried in air at 100 ℃ for 8 hours, thus obtaining the hollow copper-chromium black particles, wherein the copper-chromium black content is 35wt%, the particle size is 0.5-50 mu m, and the density is 1.6g/cm 3.
Examples 4-9 preparation of high toughness Polypropylene materials
(A) Drying polypropylene at 85 ℃ for 4 hours, and then placing the dried polypropylene, a toughening agent POE, an antioxidant beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) octadecyl propionate and tri (2, 4-di-tert-butylphenyl) phosphite into a mixer for mixing for 20 minutes to obtain a premix;
(b) Adding the premix obtained in the step (a) into a parallel double-screw extruder through a main feeder, adding the hollow copper chromium black particles prepared in the embodiment 2 into a sixth zone of the parallel double-screw extruder, and carrying out melt extrusion, wherein the processing technology of the parallel double-screw extruder is as follows: the temperature of the first area is 190 ℃, the temperature of the second area is 215 ℃, the temperature of the third area is 230 ℃, the temperature of the fourth area is 225 ℃, the temperature of the fifth area is 225 ℃, the temperature of the sixth area is 225 ℃, the temperature of the seventh area is 230 ℃, the temperature of the eighth area is 230 ℃, the temperature of the ninth area is 215 ℃, the temperature of the die head is 230 ℃, and the residence time of materials in a feed cylinder of the parallel double-screw extruder is controlled to be 1 min-3 min.
(C) And (c) bracing, cooling and granulating the extruded material obtained in the step (b) to obtain the polypropylene composition.
Wherein, the raw material components of each example are as follows:
Example 10 preparation of high toughness Polypropylene Material
This embodiment differs from embodiment 6 in that: the hollow copper chromium black particles provided in example 1 were replaced with hollow copper chromium black particles, and other raw materials and the amounts of raw materials and the preparation methods were the same as in example 6.
Example 11 preparation of high toughness Polypropylene Material
This embodiment differs from embodiment 6in that: the hollow copper chromium black particles were replaced with the hollow copper chromium black particles provided in example 3, and other raw materials and the amounts of the raw materials and the preparation methods were the same as in example 6.
Comparative example 1 preparation of Polypropylene Material
The difference between this comparative example and example 6 is that: the hollow copper chromium black particles were replaced with copper chromium black powder, and other raw materials and the amounts of raw materials and the preparation method were the same as in example 6.
Comparative example 2 preparation of Polypropylene Material
The difference between this comparative example and example 7 is that: the hollow copper chromium black particles were replaced with copper chromium black powder, and other raw materials and the amounts of raw materials and the preparation method were the same as in example 7.
Comparative example 3 preparation of Polypropylene Material
The difference between this comparative example and example 5 is that: the hollow copper chrome black particles were replaced with hollow glass bead copper chrome black, and other raw materials and raw material amounts and preparation methods were the same as in example 5.
The preparation process of the hollow glass bead copper chrome black comprises the following steps:
(1) Adding 9g of hollow glass microspheres, 14g of copper nitrate trihydrate and 50g of chromium nitrate nonahydrate into 500mL of distilled water, and uniformly dispersing to form a mixed solution;
(2) Placing the mixed solution obtained in the step (1) on a constant-temperature magnetic stirrer, stirring and heating to 60 ℃, then dropwise adding urea, adjusting the pH of the mixed solution to 6-7 under the stirring condition, and continuously stirring and heating until the water evaporation is completed, thus obtaining a hollow copper-chromium black precursor;
(3) And (3) placing the hollow copper-chromium black precursor obtained in the step (2) in an electric furnace, and calcining for 2 hours at 550 ℃ to obtain hollow copper-chromium black particles, wherein the copper-chromium black content is 60wt%, the particle size is 1-50 mu m, and the density is 2.0g/cm 3.
Comparative example 4 preparation of Polypropylene Material
The difference between this comparative example and example 6 is that: the hollow copper chrome black particles were replaced with hollow glass bead copper chrome black, and other raw materials and raw material amounts and preparation methods were the same as in example 6. The preparation method of the hollow glass microsphere copper chrome black is the same as that of comparative example 3.
The polypropylene materials obtained in the above examples and comparative examples were injection molded into plastic articles of a certain shape. And (3) carrying out laser etching on the preset area of the plastic piece according to a set shape by using laser with the wavelength of 900-1080nm and the energy of 150-300mJ/cm 2 under the scanning rate of 0.1-1mm/s according to a conventional method, carrying out chemical plating on the plastic piece subjected to laser etching, and forming a metal plating layer in the laser etching area of the plastic piece to obtain a plastic piece sample.
The plastic part samples prepared above were subjected to the following performance tests (the results are shown in Table 1):
tensile properties: the stretching rate is 50mm/min according to ASTM-D638;
impact properties: the thickness of the bars is 3.2mm according to ASTM-D256;
Adhesion test (hundred test) of metal plating on plastic part surface: according to ASTM D3359 standard
Under the conditions of room temperature of 23+/-2 ℃ and relative humidity of 50+/-5%, scribing 10X 10 small grids of 1mm multiplied by 1mm on the surface of the test sample by using a sharp blade (the blade angle is 15 DEG to 30 DEG), wherein each scribing is deep and the coating bottom layer is coated; brushing the test area cleanly by using a hairbrush; firmly adhering the tested small grid by using a 3M600 adhesive tape, and forcefully wiping the adhesive tape by using an eraser to enlarge the contact area and the strength of the adhesive tape and a tested area; the end of the tape was grasped by hand and the tape was pulled off rapidly at an angle of 60 ° in the vertical direction and 2 identical tests were performed at the same position.
And (3) result judgment: and the adhesive force is qualified when the adhesive force is more than or equal to 4B.
5B, the scribing edge is smooth, and no metal coating is dropped off at the scribing edge and the crossing point;
4B-a small piece of metal-free coating is peeled off at the cross point of the scribing line, and the total peeled-off area is less than 5%;
3B-small pieces of metal-free plating layers are peeled off at the edges and the crossing points of the scribing lines, and the total peeled-off area is between 5 and 15 percent;
2B-a piece of metal-free coating is peeled off at the edge and the cross point of the scribing line, and the total peeled-off area is 15-35%;
1B-a piece of metal plating layer is peeled off at the edge and the cross point of the scribing line, and the total peeled-off area is between 35 and 65 percent;
0B-a piece of metal-free coating is peeled off at the edge and the crossing point of the scribing line, and the total peeled-off area is more than 65 percent.
TABLE 1 Performance test results for examples 4-9 and comparative examples 1-4
The polypropylene material provided by the invention can be directly molded by laser, and has good metal coating adhesion and mechanical properties.
As can be seen from comparison of examples 6-7 and comparative examples 1-2, the polypropylene material provided by the invention has higher metal coating adhesion and better impact property, and the metal coating adhesion of the polypropylene material can reach the optimal effect of 5B by adding 4wt% of hollow copper chromium black particles; the adhesive force of the metal coating of the polypropylene material added with 4wt% of metal oxide powder can not meet the requirement, and when the addition amount of the metal oxide powder reaches 8%, the adhesive force of the metal coating can meet the qualified requirement of 4B, but the impact performance of the polypropylene material can be greatly influenced; compared with the common metal oxide powder, the hollow metal oxide particles required by the polypropylene material provided by the invention are fewer, and the obtained polypropylene material has better impact performance.
As can be seen from comparison of examples 5-6 and comparative examples 3-4, the polypropylene material provided by the invention has higher metal coating adhesion and impact performance, the adhesion of the metal coating of the polypropylene material can reach the qualification requirement of 4B by adding 3wt% of hollow copper chromium black particles, and the adhesion of the metal coating of the polypropylene material can reach the optimal effect of 5B by adding 4wt% of hollow copper chromium black particles; the adhesive force of the metal coating is only 2B, and the impact performance is also poorer than that of the example 5, and the adhesive force of the metal coating can reach 5B but the impact performance is much poorer than that of the example 6 by adding the hollow glass bead copper-chromium black of 3 wt%; this is because the hollow metal oxide is required to be calcined at a high temperature during synthesis, and the agglomeration of powder is easily caused, so that the dispersion is poor, and finally the adhesion and impact performance of the metal coating of the polypropylene material are affected.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (20)
1. The high-toughness polypropylene material is characterized by being prepared from the following raw materials in percentage by weight:
0-6% of toughening agent;
3-8% of hollow metal oxide;
0-2% of antioxidant;
Polypropylene was added to 100%;
the hollow metal oxide is obtained by coating the surface of POSS with metal oxide; the weight percentage of the metal oxide in the hollow metal oxide is 35-70%;
The preparation method of the hollow metal oxide comprises the following steps:
(1) Mixing the aminophenyl POSS and the metal salt corresponding to the metal oxide, and adding water for dissolution;
(2) Heating the mixed solution prepared in the step (1), dropwise adding a citric acid aqueous solution under stirring, adding a sol stabilizer after the dropwise adding is finished, continuing stirring until the sol is converted into gel, and stopping stirring;
(3) Drying the wet gel prepared in the step (2), and grinding into powder to obtain precursor powder;
(4) And adding water into the precursor powder for crystallization to obtain the hollow metal oxide.
2. The high-toughness polypropylene material according to claim 1, wherein the hollow metal oxide is 3-7% by weight; and/or the number of the groups of groups,
The weight percentage of the toughening agent is 2-5%; and/or the number of the groups of groups,
The weight percentage of the antioxidant is 0.2-0.5%.
3. The high-toughness polypropylene material according to claim 2, wherein the hollow metal oxide is 3-6% by weight.
4. A high-toughness polypropylene material according to claim 3, wherein the hollow metal oxide is present in an amount of 3 to 5% by weight.
5. The high-toughness polypropylene material according to claim 4, wherein the hollow metal oxide is 3.5 to 4.5% by weight.
6. The high-toughness polypropylene material according to claim 1, wherein the weight percentage of the metal oxide in the hollow metal oxide is 45-65%.
7. The high-toughness polypropylene material according to claim 6, wherein the weight percentage of the metal oxide in the hollow metal oxide is 50-60%.
8. The high-toughness polypropylene material according to claim 1, wherein the metal element in the metal oxide is one or more of copper, silver, gold, zinc, cadmium, gallium, titanium, chromium, cobalt, manganese, cerium, niobium and iron; and/or the number of the groups of groups,
The toughening agent is POE; and/or the number of the groups of groups,
The antioxidant consists of hindered phenol antioxidants and phosphite antioxidants.
9. The high-toughness polypropylene material according to claim 8, wherein the metal oxide is copper chrome black.
10. The high-toughness polypropylene material according to claim 8, wherein the hindered phenolic antioxidant and the phosphite antioxidant are the same in weight percent.
11. The high-toughness polypropylene material according to claim 8, wherein the hindered phenolic antioxidant is octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate and the phosphite antioxidant is tris (2, 4-di-tert-butylphenyl) phosphite.
12. The high-toughness polypropylene material according to claim 1, wherein the hollow metal oxide has a density of 1g/cm 3-6g/cm3; and/or the number of the groups of groups,
The particle size of the hollow metal oxide is 0.1-100 mu m.
13. The high-toughness polypropylene material according to claim 12, wherein the hollow metal oxide has a density of 1.5g/cm 3-2.7 g/cm3.
14. The high-toughness polypropylene material according to claim 12, wherein the hollow metal oxide has a particle size of 0.5 μm to 50 μm.
15. The high-toughness polypropylene material according to any one of claims 1 to 14, wherein the mass ratio of the metal salt corresponding to the metal oxide to the aminophenyl POSS is 1 to 5:1.
16. The high-toughness polypropylene material according to any one of claims 1 to 14, wherein the metal salts corresponding to the metal oxides are copper nitrate trihydrate and chromium nitrate nonahydrate.
17. The high-toughness polypropylene material according to claim 16, wherein the mass ratio of copper nitrate trihydrate to chromium nitrate nonahydrate is 1:1.5-2.5.
18. The high-toughness polypropylene material according to any one of claims 1 to 14 wherein,
The ratio of the total mass of the aminophenyl POSS and the metal salt to water in the step (1) is 1g:4mL-8mL; and/or the number of the groups of groups,
The heating temperature in the step (2) is 70-90 ℃; and/or the number of the groups of groups,
The stirring rotating speed in the step (2) is 1000r/min-1400r/min; and/or the number of the groups of groups,
The concentration of the aqueous solution of citric acid is 0.07g/mL-0.10g/mL, and the dripping amount of the aqueous solution of citric acid is the same as the water added in the step (1); and/or the number of the groups of groups,
The sol stabilizer is glycol, and the added volume of the sol stabilizer is 0.1% -0.3% of the total volume of the citric acid aqueous solution and the water in the step (1); and/or the number of the groups of groups,
The drying in the step (3) is carried out under the conditions that the vacuum degree is minus 0.5Mpa to minus 0.7Mpa and the temperature is 70 ℃ to 90 ℃; and/or the number of the groups of groups,
The step (4) comprises: and (3) filling the precursor powder into a reaction kettle, adding water, uniformly stirring, screwing a kettle cover, crystallizing for 2-7 days under the conditions of the pressure of 15-20 MPa and the temperature of 280-320 ℃, filtering, washing and drying the product to obtain the hollow metal oxide.
19. A method for preparing a high-toughness polypropylene material according to any one of claims 1 to 18, comprising the steps of:
(a) Mixing the polypropylene with the toughening agent and the antioxidant after drying to obtain a premix;
(b) Adding the premix obtained in the step (a) into a parallel double-screw extruder through a main feeder, adding the hollow metal oxide in the lateral direction of the parallel double-screw extruder, and carrying out melt extrusion;
(c) And (c) bracing, cooling and granulating the extruded material obtained in the step (b) to obtain the high-toughness polypropylene material.
20. The method of claim 19, wherein the drying conditions of step (a) comprise: the temperature is 80-90 ℃ and the time is 3-5 h; and/or the number of the groups of groups,
The processing conditions of the parallel double-screw extruder comprise: the temperature of the first area is 180-200 ℃, the temperature of the second area is 200-225 ℃, the temperature of the third area is 220-235 ℃, the temperature of the fourth area is 220-235 ℃, the temperature of the fifth area is 220-235 ℃, the temperature of the sixth area is 220-235 ℃, the temperature of the seventh area is 220-235 ℃, the temperature of the eighth area is 220-235 ℃, the temperature of the ninth area is 210-225 ℃, the temperature of the die head is 220-235 ℃, and the residence time of the materials in the charging barrel of the parallel double-screw extruder is controlled to be 1-3 minutes.
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