CN111808393A - High-strength high-toughness PMMA (polymethyl methacrylate) super-hydrophobic composite material for piano white key skins - Google Patents
High-strength high-toughness PMMA (polymethyl methacrylate) super-hydrophobic composite material for piano white key skins Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
- C08L33/12—Homopolymers or copolymers of methyl methacrylate
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
The invention discloses a high-strength high-toughness PMMA (polymethyl methacrylate) super-hydrophobic composite material for piano white key skins in the technical field of hydrophobic materials, which comprises the following raw materials in parts by weight: 20-30 parts of nano calcium carbonate, 5-10 parts of triethylamine, 3-7 parts of polyphosphazene, 40-50 parts of tetrahydrofuran, 50-80 parts of absolute ethyl alcohol, 10-15 parts of bisphenol S, 70-100 parts of PMMA granules, 15-25 parts of two-block copolymer polystyrene-polymethyl methacrylate and 10-15 parts of silicone powder, the nano calcium carbonate particles and the two-block copolymer polystyrene-polymethyl methacrylate are wrapped by adding the polyphosphazene, can greatly improve the strength and toughness of the PMMA composite material, improves the smoothness, glossiness, touch and abrasion resistance of the surface of a plastic product by adding the silicone powder, and meanwhile, the composite material is endowed with the super-sulfur water performance, so that the surface of a plastic product has certain antifouling performance, the surface cracking phenomenon is reduced, and the composite material is suitable for piano white key skins and meets the manufacturing and using requirements of various piano white keys.
Description
Technical Field
The invention relates to the technical field of hydrophobic materials, in particular to a high-strength high-toughness PMMA (polymethyl methacrylate) super-hydrophobic composite material for a piano white key skin.
Background
The musical instrument is used as a carrier for performing music, expressing and transmitting human emotion, the cultural significance of the musical instrument exceeds that of a playing tool, and a piano with the 'king of musical instrument' plays an important role in various music forms such as fashion, rock, jazz and classical music.
Pianos are the most complex and precise instruments to be produced in the world, except for organs, and 300 production processes and 9000 parts are required for producing one piano. Among them, piano keys are one of the most important components, and piano keys are classified into white keys and black keys. In general, a white key is composed of a key body and a white key skin. The white key skin is a separately produced part, and then attached to the key body for distinguishing from the black keys. Most piano key skins used in the market are formed by plastic injection molding, and a small part of high-grade piano key skins also adopt black wood or white ivory as manufacturing materials of the piano key skins. Since black wood, ivory, and the like are expensive and difficult to maintain, polymethyl methacrylate (PMMA) plastic is often used as a manufacturing raw material for piano white keys on the market.
However, the piano white key skins on the market have some major problems in manufacturing, transportation, finished products, and the like: in the transportation process of the articles, the articles are collided in different degrees, the piano white key components are not unexpected, even under the condition of tight packaging, the piano white keys are scratched and cracked due to the fact that the collision and the self resistance and toughness of part of the piano white keys are poor, so that when the piano white key components are conveyed to a buyer, about 70% of the piano white key components are mostly qualified products, and resource waste in all aspects is indirectly caused; the product performance is lower, the service life is shorter, the piano white key skin product is easy to crack in autumn and winter, and the PMMA product surface can react with ethanol after being wiped by using ethanol and cause swelling and cracking.
Based on the PMMA super-hydrophobic composite material, the invention particularly relates to a high-strength high-toughness PMMA super-hydrophobic composite material for a piano white key skin, and aims to solve the problems.
Disclosure of Invention
The invention aims to provide a high-strength high-toughness PMMA (polymethyl methacrylate) super-hydrophobic composite material for a piano white key skin, which is used for solving the problems in the background technology.
In order to achieve the purpose, the invention provides the following technical scheme: a high-strength high-toughness PMMA (polymethyl methacrylate) super-hydrophobic composite material for a piano white key skin comprises the following raw materials in parts by weight: 20-30 parts of nano calcium carbonate, 5-10 parts of triethylamine, 3-7 parts of polyphosphazene, 40-50 parts of tetrahydrofuran, 50-80 parts of absolute ethyl alcohol, 10-15 parts of bisphenol S, 70-100 parts of PMMA granules, 15-25 parts of two-block copolymer polystyrene-polymethyl methacrylate and 10-15 parts of silicone powder.
The high-strength high-toughness PMMA super-hydrophobic composite material for the piano white key skin disclosed by the invention further comprises the nano calcium carbonate, wherein the average particle size of the nano calcium carbonate is 10-80 nm.
The invention relates to a high-strength high-toughness PMMA (polymethyl methacrylate) super-hydrophobic composite material for piano white key skins, and further, the preparation method of the super-hydrophobic composite material comprises the following steps:
(1) mixing tetrahydrofuran and absolute ethyl alcohol, adding the mixture into a container, adding nano calcium carbonate, triethylamine and polyphosphazene into the container, ultrasonically mixing, adding bisphenol S, washing the filtered precipitate for multiple times by using a tetrahydrofuran solution, drying the obtained solid in vacuum, and carrying out chemical crosslinking reaction to obtain nano particles of the polyphosphazene-coated nano calcium carbonate;
(2) mixing the dried PMMA granules with nano particles of polyphosphazene-coated nano calcium carbonate, adding diblock copolymer polystyrene-polymethyl methacrylate and silicone powder, uniformly mixing in a high-speed mixer, adding into a double-screw extruder for melt blending, extruding and granulating, and then drying in vacuum to obtain the super-hydrophobic composite material.
The invention relates to a high-strength high-toughness PMMA super-hydrophobic composite material for piano white key skins, which is characterized in that the vacuum drying conditions in the step (1) are as follows: the drying temperature is 90 ℃ and the drying time is 12 h.
The invention relates to a high-strength high-toughness PMMA super-hydrophobic composite material for piano white key skins, which is characterized in that the ultrasonic mixing conditions in the step (1) are as follows: the ultrasonic power is 150W, the ultrasonic temperature is 10-50 ℃, and the ultrasonic time is 3 h.
The high-strength high-toughness PMMA super-hydrophobic composite material for the piano white key skin disclosed by the invention further comprises the step (2) that the stirring speed of a high-speed mixer is 1000-3000rpm, and the stirring temperature is 0-60 ℃.
The invention relates to a high-strength high-toughness PMMA super-hydrophobic composite material for piano white key skins, which is characterized in that the vacuum drying conditions in the step (2) are as follows: the drying temperature is 90 ℃ and the drying time is 6 h.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, polyphosphazene is adopted to wrap nano calcium carbonate particles as a toughening agent, and meanwhile, the diblock copolymer polystyrene-polymethyl methacrylate is added as a compatilizer, so that the better compatibility of the nano filler and the PMMA matrix enhances the dispersion effect of the nano filler in the PMMA matrix, the strength and toughness of the PMMA composite material can be greatly improved, the compatibilization efficiency is improved, and high notch impact strength and tensile strength are obtained; the silicone powder with a certain proportion is added, so that the smoothness, the glossiness, the touch feeling and the wear resistance of the surface of the plastic product are improved, and the composite material is endowed with an ultra-sulfur water performance, so that the surface of the plastic product has a certain antifouling performance, the alcohol resistance of the surface of the product is improved, the corrosion to the surface of the product during alcohol wiping is resisted, the surface micro-stress cracking phenomenon during swelling is reduced, and the preparation of the surface of a highlight non-mark product is realized; is suitable for the piano white key skin, and meets the manufacturing and using requirements of various piano white keys.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
a high-strength high-toughness PMMA (polymethyl methacrylate) super-hydrophobic composite material for a piano white key skin is prepared by the following steps:
(1) mixing 45 parts of tetrahydrofuran and 65 parts of absolute ethyl alcohol, adding the mixture into a container, adding 25 parts of nano calcium carbonate, 9 parts of triethylamine and 5 parts of polyphosphazene into the container, carrying out ultrasonic mixing for 3 hours at the ultrasonic power of 150W and the ultrasonic temperature of 35 ℃, adding 14 parts of bisphenol S, washing the filtered precipitate for multiple times by using a tetrahydrofuran solution, carrying out vacuum drying on the obtained solid for 12 hours at 90 ℃, and carrying out chemical crosslinking reaction to obtain polyphosphazene-coated nano calcium carbonate nanoparticles, wherein the average particle size of the nano calcium carbonate is 50 nm;
(2) and mixing 75 parts of dried PMMA granules with nano particles of polyphosphazene-coated nano calcium carbonate, adding 23 parts of diblock copolymer polystyrene-polymethyl methacrylate and 13 parts of silicone powder, uniformly mixing in a high-speed mixer at the stirring speed of 2000rpm and the stirring temperature of 20 ℃, adding into a double-screw extruder for melt blending, extruding and granulating, and drying in vacuum at the temperature of 90 ℃ for 6 hours to obtain the super-hydrophobic composite material.
Example 2:
a high-strength high-toughness PMMA (polymethyl methacrylate) super-hydrophobic composite material for a piano white key skin is prepared by the following steps:
(1) mixing 40 parts of tetrahydrofuran and 55 parts of absolute ethyl alcohol, adding the mixture into a container, adding 30 parts of nano calcium carbonate, 8 parts of triethylamine and 3 parts of polyphosphazene into the container, carrying out ultrasonic mixing for 3 hours at the ultrasonic power of 150W and the ultrasonic temperature of 25 ℃, adding 10 parts of bisphenol S, washing the filtered precipitate for multiple times by using a tetrahydrofuran solution, carrying out vacuum drying on the obtained solid for 12 hours at 90 ℃, and carrying out chemical crosslinking reaction to obtain polyphosphazene-coated nano calcium carbonate nanoparticles, wherein the average particle size of the nano calcium carbonate is 20 nm;
(2) mixing 85 parts of dried PMMA granules with nano particles of polyphosphazene-coated nano calcium carbonate, adding 20 parts of diblock copolymer polystyrene-polymethyl methacrylate and 12 parts of silicone powder, uniformly mixing in a high-speed mixer at the stirring speed of 1000rpm and the stirring temperature of 30 ℃, adding into a double-screw extruder for melt blending, extruding and granulating, and drying in vacuum at 90 ℃ for 6 hours to obtain the super-hydrophobic composite material.
Example 3:
a high-strength high-toughness PMMA (polymethyl methacrylate) super-hydrophobic composite material for a piano white key skin is prepared by the following steps:
(1) mixing 50 parts of tetrahydrofuran and 60 parts of absolute ethyl alcohol, adding the mixture into a container, adding 20 parts of nano calcium carbonate, 6 parts of triethylamine and 4 parts of polyphosphazene into the container, carrying out ultrasonic mixing for 3 hours at the ultrasonic power of 150W and the ultrasonic temperature of 20 ℃, adding 12 parts of bisphenol S, washing the filtered precipitate for multiple times by using a tetrahydrofuran solution, carrying out vacuum drying on the obtained solid for 12 hours at 90 ℃, and carrying out chemical crosslinking reaction to obtain polyphosphazene-coated nano calcium carbonate nanoparticles, wherein the average particle size of the nano calcium carbonate is 80 nm;
(2) mixing 90 parts of dried PMMA granules with nano particles of polyphosphazene-coated nano calcium carbonate, adding 15 parts of diblock copolymer polystyrene-polymethyl methacrylate and 10 parts of silicone powder, uniformly mixing in a high-speed mixer at the stirring speed of 3000rpm and the stirring temperature of 60 ℃, adding into a double-screw extruder for melt blending, extruding and granulating, and drying in vacuum at 90 ℃ for 6 hours to obtain the super-hydrophobic composite material.
Example 4:
a high-strength high-toughness PMMA (polymethyl methacrylate) super-hydrophobic composite material for a piano white key skin is prepared by the following steps:
(1) mixing 42 parts of tetrahydrofuran and 70 parts of absolute ethyl alcohol, adding the mixture into a container, adding 27 parts of nano calcium carbonate, 7 parts of triethylamine and 7 parts of polyphosphazene into the container, carrying out ultrasonic mixing for 3 hours at the ultrasonic power of 150W and the ultrasonic temperature of 10 ℃, adding 15 parts of bisphenol S, washing the filtered precipitate for multiple times by using a tetrahydrofuran solution, carrying out vacuum drying on the obtained solid for 12 hours at 90 ℃, and carrying out chemical crosslinking reaction to obtain polyphosphazene-coated nano calcium carbonate nanoparticles, wherein the average particle size of the nano calcium carbonate is 30 nm;
(2) mixing 100 parts of dried PMMA granules with nano particles of polyphosphazene-coated nano calcium carbonate, adding 25 parts of diblock copolymer polystyrene-polymethyl methacrylate and 14 parts of silicone powder, uniformly mixing in a high-speed mixer at the stirring speed of 1500rpm and the stirring temperature of 0 ℃, adding into a double-screw extruder for melt blending, extruding and granulating, and drying in vacuum at the temperature of 90 ℃ for 6 hours to obtain the super-hydrophobic composite material.
Example 5:
a high-strength high-toughness PMMA (polymethyl methacrylate) super-hydrophobic composite material for a piano white key skin is prepared by the following steps:
(1) mixing 47 parts of tetrahydrofuran and 80 parts of absolute ethyl alcohol, adding the mixture into a container, adding 22 parts of nano calcium carbonate, 5 parts of triethylamine and 6 parts of polyphosphazene into the container, carrying out ultrasonic mixing for 3 hours at the ultrasonic power of 150W and the ultrasonic temperature of 50 ℃, adding 13 parts of bisphenol S, washing the filtered precipitate for multiple times by using a tetrahydrofuran solution, carrying out vacuum drying on the obtained solid for 12 hours at 90 ℃, and carrying out chemical crosslinking reaction to obtain polyphosphazene-coated nano calcium carbonate nanoparticles, wherein the average particle size of the nano calcium carbonate is 10 nm;
(2) and mixing 70 parts of dried PMMA granules with nano particles of polyphosphazene-coated nano calcium carbonate, adding 17 parts of diblock copolymer polystyrene-polymethyl methacrylate and 11 parts of silicone powder, uniformly mixing in a high-speed mixer at the stirring speed of 2500rpm and the stirring temperature of 10 ℃, adding into a double-screw extruder for melt blending, extruding and granulating, and drying in vacuum at the temperature of 90 ℃ for 6 hours to obtain the super-hydrophobic composite material.
Example 6:
a high-strength high-toughness PMMA (polymethyl methacrylate) super-hydrophobic composite material for a piano white key skin is prepared by the following steps:
(1) mixing 46 parts of tetrahydrofuran and 50 parts of absolute ethyl alcohol, adding the mixture into a container, adding 24 parts of nano calcium carbonate, 10 parts of triethylamine and 5 parts of polyphosphazene into the container, carrying out ultrasonic mixing for 3 hours at the ultrasonic power of 150W and the ultrasonic temperature of 30 ℃, adding 11 parts of bisphenol S, washing the filtered precipitate for multiple times by using a tetrahydrofuran solution, carrying out vacuum drying on the obtained solid for 12 hours at 90 ℃, and carrying out chemical crosslinking reaction to obtain polyphosphazene-coated nano calcium carbonate nanoparticles, wherein the average particle size of the nano calcium carbonate is 60 nm;
(2) and mixing 80 parts of dried PMMA granules with nano particles of polyphosphazene-coated nano calcium carbonate, adding 22 parts of diblock copolymer polystyrene-polymethyl methacrylate and 15 parts of silicone powder, uniformly mixing in a high-speed mixer at the stirring speed of 2000rpm at the stirring temperature of 50 ℃, adding into a double-screw extruder for melt blending, extruding and granulating, and drying in vacuum at the temperature of 90 ℃ for 6 hours to obtain the super-hydrophobic composite material.
And (3) performance testing:
injecting the super-hydrophobic composite materials prepared in the embodiments 1-6 into standard samples 1-6 through a precision injection molding machine, directly injecting PMMA granules into a standard sample 7 through the precision injection molding machine by a control group, and carrying out performance test on the standard samples 1-7: according to ISO 527-2: 1996 and ISO 179-2: 1999 test the tensile strength, elongation at break, impact strength of the standard samples 1-7; the standard samples 1-7 were immersed in an alcohol at-20 ℃ for 30min, taken out and air-dried naturally, and after 3 days of use, surface cracking and antifouling were observed to obtain table 1.
Table 1:
as can be seen from Table 1, the PMMA super-hydrophobic composite material prepared by the invention has high strength and toughness, good mechanical property, anti-cracking property and anti-fouling property.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.
Claims (7)
1. The high-strength high-toughness PMMA super-hydrophobic composite material for the white bond skin of the piano is characterized by comprising the following raw materials in parts by weight: 20-30 parts of nano calcium carbonate, 5-10 parts of triethylamine, 3-7 parts of polyphosphazene, 40-50 parts of tetrahydrofuran, 50-80 parts of absolute ethyl alcohol, 10-15 parts of bisphenol S, 70-100 parts of PMMA granules, 15-25 parts of two-block copolymer polystyrene-polymethyl methacrylate and 10-15 parts of silicone powder.
2. The high-strength high-toughness PMMA super-hydrophobic composite material for the white bond skin of the piano according to claim 1, is characterized in that: the average grain diameter of the nano calcium carbonate is 10-80 nm.
3. The PMMA super-hydrophobic composite material with high strength and toughness for the white bond skin of the piano as claimed in claim 1 or 2, wherein the preparation method of the super-hydrophobic composite material comprises the following steps:
(1) mixing tetrahydrofuran and absolute ethyl alcohol, adding the mixture into a container, adding nano calcium carbonate, triethylamine and polyphosphazene into the container, ultrasonically mixing, adding bisphenol S, washing the filtered precipitate for multiple times by using a tetrahydrofuran solution, drying the obtained solid in vacuum, and carrying out chemical crosslinking reaction to obtain nano particles of the polyphosphazene-coated nano calcium carbonate;
(2) mixing the dried PMMA granules with nano particles of polyphosphazene-coated nano calcium carbonate, adding diblock copolymer polystyrene-polymethyl methacrylate and silicone powder, uniformly mixing in a high-speed mixer, adding into a double-screw extruder for melt blending, extruding and granulating, and then drying in vacuum to obtain the super-hydrophobic composite material.
4. The high-strength high-toughness PMMA super-hydrophobic composite material for the white bond skin of the piano according to claim 3, is characterized in that: the vacuum drying conditions in the step (1) are as follows: the drying temperature is 90 ℃ and the drying time is 12 h.
5. The high-strength high-toughness PMMA super-hydrophobic composite material for the white bond skin of the piano according to claim 3, is characterized in that: the ultrasonic mixing conditions in the step (1) are as follows: the ultrasonic power is 150W, the ultrasonic temperature is 10-50 ℃, and the ultrasonic time is 3 h.
6. The high-strength high-toughness PMMA super-hydrophobic composite material for the white bond skin of the piano according to claim 3, is characterized in that: the stirring speed of the high-speed mixer in the step (2) is 1000-3000rpm, and the stirring temperature is 0-60 ℃.
7. The high-strength high-toughness PMMA super-hydrophobic composite material for the white bond skin of the piano according to claim 3, is characterized in that: the vacuum drying conditions in the step (2) are as follows: the drying temperature is 90 ℃ and the drying time is 6 h.
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| CN202010704307.5A CN111808393A (en) | 2020-07-21 | 2020-07-21 | High-strength high-toughness PMMA (polymethyl methacrylate) super-hydrophobic composite material for piano white key skins |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115716965A (en) * | 2021-08-24 | 2023-02-28 | 北京乐器研究所 | Preparation method of ivory-imitated material |
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| CN102190846A (en) * | 2011-01-28 | 2011-09-21 | 上海锦湖日丽塑料有限公司 | Antiscratch resin and preparation method thereof |
| CN107955309A (en) * | 2017-12-05 | 2018-04-24 | 四川力智久创知识产权运营有限公司 | A kind of ageing-resistant modified material of polymethyl methacrylate and preparation method thereof |
| CN109206817A (en) * | 2018-10-30 | 2019-01-15 | 苏州骏宝电子有限公司 | A kind of composite plastic and preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102190846A (en) * | 2011-01-28 | 2011-09-21 | 上海锦湖日丽塑料有限公司 | Antiscratch resin and preparation method thereof |
| CN107955309A (en) * | 2017-12-05 | 2018-04-24 | 四川力智久创知识产权运营有限公司 | A kind of ageing-resistant modified material of polymethyl methacrylate and preparation method thereof |
| CN109206817A (en) * | 2018-10-30 | 2019-01-15 | 苏州骏宝电子有限公司 | A kind of composite plastic and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115716965A (en) * | 2021-08-24 | 2023-02-28 | 北京乐器研究所 | Preparation method of ivory-imitated material |
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Application publication date: 20201023 |