CN113278181A - Self-cleaning PETG material and application thereof - Google Patents
Self-cleaning PETG material and application thereof Download PDFInfo
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- CN113278181A CN113278181A CN202110072989.7A CN202110072989A CN113278181A CN 113278181 A CN113278181 A CN 113278181A CN 202110072989 A CN202110072989 A CN 202110072989A CN 113278181 A CN113278181 A CN 113278181A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
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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
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/003—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
Abstract
The invention discloses a self-cleaning PETG material which is a three-layer composite material, wherein a PETG layer is arranged in the middle layer, and the rest two layers are nano coatings. The invention has good self-cleaning function and can be used for various electronic components and optical equipment.
Description
Technical Field
The invention relates to the field of PETG, in particular to a self-cleaning PETG material.
Background
PETG is a very good material, which is the product of polycondensation of three monomers, terephthalic acid (PTA), Ethylene Glycol (EG) and 1, 4-Cyclohexanedimethanol (CHDM). The PETG sheet material has outstanding toughness and high impact strength, the impact strength of the PETG sheet material is 3-10 times that of modified polyacrylate, the PETG sheet material has a wide processing range, high mechanical strength and excellent flexibility, and compared with PVC, the PETG sheet material has the advantages of high transparency, good gloss, easiness in printing and environmental friendliness.
The demand of materials in electronic components is higher and higher, the requirement on the self-cleaning function of PETG is high at present, the mainstream self-cleaning means at present is to add a fluorine-containing auxiliary agent or modify the main body by fluorine, but fluorine element is also halogen, and the control of the electronic components on the halogen is very strict, so that the PETG needs to be subjected to self-cleaning treatment by other means.
Disclosure of Invention
To solve the above problems. The invention discloses a self-cleaning PETG material.
The invention relates to a self-cleaning PETG material which is a three-layer composite material, wherein the middle layer is a PETG layer, the remaining two layers are nano coatings, and the nano coatings consist of nano particles and have the diameter of 100-200 nm.
The nano particles form a microstructure on the pattern layer due to the small size characteristic of the nano particles, and can well play a self-cleaning role.
As a further scheme of the invention, the proportion of the dihydric alcohol 1,4 cyclohexane dimethanol and the glycol in the PETG resin used in the PETG layer in the self-cleaning PETG material is 5: 5.
As a further scheme of the invention, the antioxidant used in the PETG layer in the self-cleaning PETG material is one or more of antioxidant 1010, antioxidant 626 and antioxidant 1029.
As a further scheme of the invention, the lubricant used in the PETG layer in the self-cleaning PETG material is one or more of HONEYWELL PETG 400A, pentaerythritol stearate, myristyl stearate, calcium stearate and magnesium stearate.
As a further scheme of the invention, the nano particles in the self-cleaning PETG material are three-layer self-assembled microspheres polymerized by an RATF method.
RAFT is an abbreviation for reversible addition-fragmentation chain transfer polymerization, a living, Controlled Radical Polymerization (CRP).
As a further scheme of the invention, the first layer of the three-layer self-assembled microsphere is phenyl methacrylate, and the structure is as follows:
as a further scheme of the invention, the second layer of the polymeric monomer of the three-layer self-assembled microsphere is N- (2-hydroxypropyl) methacrylamide, and the structure is shown as follows:
as a further scheme of the invention, the synthesis method of the N- (2-hydroxypropyl) methacrylamide comprises the following steps of reacting acryloyl chloride with isopropanolamine:
adding isopropanolamine into a reactor containing tetrahydrofuran, placing the reactor into an ethanol and dry ice mixing system, and reducing the temperature of the system to-60 ℃.
Slowly dripping methacryloyl chloride into the system, keeping the temperature of the system not higher than-50 ℃, and continuously stirring after finishing dripping to naturally recover the system to the room temperature. Separating the system by column chromatography to obtain N-isopropyl-hydroxypropyl methacrylamide
As a further scheme of the invention, the three-layer self-assembly microsphere of the self-cleaning PETG material nano particle is characterized in that a third layer of polymerized monomer is resorcinol methacrylate, and the structure is as follows:
as a further aspect of the present invention, a method for synthesizing the third layer structure of the present invention comprises: reacting 5-bromoresorcinol with potassium methacrylate, and removing the produced potassium bromide to obtain the final product.
As a further scheme of the invention, the RATF method polymerization used by the self-cleaning PETG material nano-particles is carried out, and the initiator is 2,4, 6-trimethyl benzoyl phenyl ethyl phosphonate.
As a further scheme of the invention, the RATF method used by the self-cleaning PETG material nano-particles is used for polymerization, the chain transfer agent is ETPA, and the structure is as follows:
as a further scheme of the invention, the coating mode of the self-cleaning PETG material is to treat the surface of the PETG plate by Plasma and use the precision spraying nano particle emulsion to remove water to obtain the required self-cleaning PETG material.
As a further scheme of the invention, the self-cleaning PETG material has a very good self-cleaning function and can be industrially used for various electronic components and optical equipment.
The technical scheme provided by the invention has the beneficial effects that:
the self-made nano particles are coated on the surface layer of PETG, so that the water contact angle of the system can exceed 150 degrees, and a good self-cleaning effect is achieved.
The PETG surface layer treated by the Plasma can combine the nano particles better, and the self-cleaning effect is longer.
The tail end of the nano particle is a phenol group with a certain positive charge, so that certain electrostatic repulsion can be generated, and the self-cleaning effect is enhanced.
Drawings
FIG. 1 is a gel permeation chromatography spectrum of example 1, step 1;
FIG. 2 is a gel permeation chromatography spectrum of step 2 of example 1;
FIG. 3 is a gel permeation chromatography spectrum of example 1, step 3;
fig. 4 is a morphology image of the nanomaterial prepared in example 1 under a seemefly prism E SEM scanning electron microscope.
Detailed description of the invention
The present invention will be further described below by way of specific examples.
In the following examples, those whose operations are not subject to the conditions indicated, are carried out according to the conventional conditions or conditions recommended by the manufacturer. The raw materials except the antistatic polymer in the scheme of the invention are purchased from Chinese medicines and alatin.
Preparing a PETG plate:
100 parts of PETG material with the weight average molecular weight of about 25 ten thousand (wherein the molar ratio of ethylene glycol to 1,4 cyclohexanedimethanol is 5: 5), 0.2 part of antioxidant 1010 and 0.4 part of lubricant HONEYWELL polyethylene wax 400A are added into a high-speed mixer and stirred at the rotating speed of 600rpm for at least more than 20min until the mixture is uniformly stirred. Feeding into a double-screw extruder, and extruding at 230 deg.C to obtain master batch.
A plate having a thickness of 4.5mm was prepared by extrusion.
Example 1
All manipulations were carried out in the yellow region.
11.34g of phenyl methacrylate, 0.21g of a chain transfer agent ETPA and 22g of ultrapure water were charged into a reactor, the pH was adjusted to 2 to 3 by adding hydrochloric acid, and the air in the system was replaced with argon gas by using a double calandria. 0.316g of the initiator ethyl 2,4, 6-trimethylbenzoylphenylphosphonate was added in one portion to the reactor, and the UV lamp was removed immediately after 30 minutes of irradiation with the UV lamp.
10.01g of N- (2-hydroxypropyl) methacrylamide and 20g of ultrapure water were added to the reactor, hydrochloric acid was further added to adjust the pH to 2-3, 0.316g of the initiator ethyl 2,4, 6-trimethylbenzoylphenylphosphonate was added to the reactor in one portion, and the ultraviolet lamp was removed immediately after 30 minutes of irradiation with the ultraviolet lamp.
11.75g of resorcinol methacrylate 20g of ultrapure water was charged into the reactor, hydrochloric acid was further added to adjust the pH to 2 to 3, 0.316g of ethyl 2,4, 6-trimethylbenzoylphenylphosphonate as an initiator was added to the reactor in one portion, and the active reaction was terminated by passing air through the reactor after irradiating with an ultraviolet lamp for 60 minutes.
Example 2
All manipulations were carried out in the yellow region.
16.2g of phenyl methacrylate, 0.21g of a chain transfer agent ETPA and 32g of ultrapure water were charged into a reactor, the pH was adjusted to 2 to 3 by adding hydrochloric acid, and the air in the system was replaced with argon gas by using a double calandria. 0.316g of the initiator ethyl 2,4, 6-trimethylbenzoylphenylphosphonate was added in one portion to the reactor, and the UV lamp was removed immediately after 30 minutes of irradiation with the UV lamp.
21.45g of N- (2-hydroxypropyl) methacrylamide and 42g of ultrapure water were added to the reactor, hydrochloric acid was further added to adjust the pH to 2-3, 0.316g of the initiator ethyl 2,4, 6-trimethylbenzoylphenylphosphonate was added to the reactor in one portion, and the UV lamp was removed immediately after 30 minutes of irradiation with the UV lamp.
7.05g of resorcinol methacrylate 14g of ultrapure water was charged into the reactor, hydrochloric acid was further added to adjust the pH to 2 to 3, 0.316g of ethyl 2,4, 6-trimethylbenzoylphenylphosphonate as an initiator was added to the reactor in one portion, and the active reaction was terminated by passing air through the reactor after irradiating with an ultraviolet lamp for 60 minutes.
Example 3
All manipulations were carried out in the yellow region.
8.91g of phenyl methacrylate, 0.21g of a chain transfer agent ETPA and 18g of ultrapure water were charged into a reactor, the pH was adjusted to 2 to 3 by adding hydrochloric acid, and the air in the system was replaced with argon gas by using a double calandria. 0.316g of the initiator ethyl 2,4, 6-trimethylbenzoylphenylphosphonate was added in one portion to the reactor, and the UV lamp was removed immediately after 30 minutes of irradiation with the UV lamp.
3.29g of N- (2-hydroxypropyl) methacrylamide and 6.5g of ultrapure water were added to the reactor, hydrochloric acid was further added to adjust the pH to 2-3, 0.316g of the initiator ethyl 2,4, 6-trimethylbenzoylphenylphosphonate was added to the reactor in one portion, and the ultraviolet lamp was removed immediately after 30 minutes of irradiation with the ultraviolet lamp.
10.57g of resorcinol methacrylate 21g of ultrapure water was charged into the reactor, hydrochloric acid was further added to adjust the pH to 2 to 3, 0.316g of ethyl 2,4, 6-trimethylbenzoylphenylphosphonate as an initiator was added to the reactor in one portion, and the active reaction was terminated by passing air through the reactor after irradiating with an ultraviolet lamp for 60 minutes.
Example 4
All manipulations were carried out in the yellow region.
3.72g of phenyl methacrylate, 0.21g of a chain transfer agent ETPA and 7g of ultrapure water were charged into a reactor, the pH was adjusted to 2 to 3 by adding hydrochloric acid, and the air in the system was replaced with argon gas by using a double calandria. 0.316g of the initiator ethyl 2,4, 6-trimethylbenzoylphenylphosphonate was added in one portion to the reactor, and the UV lamp was removed immediately after 30 minutes of irradiation with the UV lamp.
4.29g of N- (2-hydroxypropyl) methacrylamide and 9g of ultrapure water were added to the reactor, hydrochloric acid was further added to adjust the pH to 2-3, 0.316g of the initiator ethyl 2,4, 6-trimethylbenzoylphenylphosphonate was added to the reactor in one portion, and the UV lamp was removed immediately after 30 minutes of irradiation with the UV lamp.
9.4g of resorcinol methacrylate 19g of ultrapure water was charged into the reactor, hydrochloric acid was further added to adjust the pH to 2 to 3, 0.316g of ethyl 2,4, 6-trimethylbenzoylphenylphosphonate as an initiator was added to the reactor in one portion, and the active reaction was terminated by passing air through the reactor after irradiating with an ultraviolet lamp for 60 minutes.
Example 5
All manipulations were carried out in the yellow region.
11.34g of phenyl methacrylate, 0.21g of a chain transfer agent ETPA and 22g of ultrapure water were charged into a reactor, the pH was adjusted to 2 to 3 by adding hydrochloric acid, and the air in the system was replaced with argon gas by using a double calandria. 0.316g of the initiator ethyl 2,4, 6-trimethylbenzoylphenylphosphonate was added in one portion to the reactor, and the UV lamp was removed immediately after 30 minutes of irradiation with the UV lamp.
14.3g of N- (2-hydroxypropyl) methacrylamide and 29g of ultrapure water were added to the reactor, hydrochloric acid was further added to adjust the pH to 2-3, 0.316g of the initiator ethyl 2,4, 6-trimethylbenzoylphenylphosphonate was added in one portion to the reactor, and the UV lamp was removed immediately after 30 minutes of irradiation with the UV lamp.
18.8g of resorcinol methacrylate 39g of ultrapure water was charged into the reactor, hydrochloric acid was further added to adjust the pH to 2 to 3, 0.316g of ethyl 2,4, 6-trimethylbenzoylphenylphosphonate as an initiator was added to the reactor in one portion, and the active reaction was terminated by passing air through the reactor after irradiating with an ultraviolet lamp for 60 minutes.
The above description is only exemplary of the present invention and should not be taken as limiting the scope of the present invention, as any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
The invention mainly relates to a self-cleaning PETG material and application thereof, so that the particle size of each embodiment and the water contact angle after spraying are tested to represent the self-cleaning effect, and the molecular weight data of embodiment 1 are tested to represent the dispersion coefficient of the nano particles.
As shown in fig. 1, 2 and 3, it can be seen from the above figures that the nanoparticles polymerized using the RATF method of the present invention have very good dispersibility.
And (3) particle size testing:
particle size was tested using a semer fly prism E SEM scanning electron microscope. As shown in fig. 4.
Water contact angle test:
the test was carried out using a water drop angle measuring instrument model SL200 KS.
| Particle size | Water contact angle | |
| Example 1 | 159um | 155° |
| Example 2 | 193nm | 151° |
| Example 3 | 145nm | 157° |
| Example 4 | 131nm | 159° |
| Example 5 | 182nm | 152° |
As can be seen from the above table, the invention prepares ultrafine nanoparticles, achieves very high water contact angle, and has excellent self-cleaning performance.
Claims (12)
1. The invention relates to a self-cleaning PETG material which is a three-layer composite material, wherein the middle layer is a PETG layer, the remaining two layers are nano coatings, and the nano coatings consist of nano particles and have the diameter of 100-200 nm.
2. The PETG resin used for the PETG layer in the self-cleaning PETG material is characterized in that the ratio of 1, 4-cyclohexane dimethanol to glycol in the PETG resin is 5: 5.
3. The self-cleaning PETG material of the invention is characterized in that the antioxidant used in the PETG layer is one or more of antioxidant 1010, antioxidant 626 and antioxidant 1029.
4. The self-cleaning PETG material of the invention is characterized in that the lubricant used for the PETG layer is one or more of HONEYWELL PETG polyethylene wax 400A, pentaerythritol stearate, tetradecyl stearate, calcium stearate and magnesium stearate.
5. The high toughness PETG material according to claim 1, wherein the nano-ions in the high toughness PETG material are three-layer self-assembled microspheres polymerized by the RATF method.
6. The three-layer self-assembled microsphere according to claim 5, wherein the first layer is phenyl methacrylate and has the following structure:
7. the three-layer self-assembled microsphere of claim 5, wherein the second layer is N- (2-hydroxypropyl) methacrylamide, having the following structure:
8. the three-layer self-assembled microsphere of claim 5, wherein the third layer has the following structure:
9. the N- (2-hydroxypropyl) methacrylamide according to claim 7, prepared by reacting acryloyl chloride with isopropanolamine.
10. The RATF process polymerization of claim 5 wherein the initiator is ethyl 2,4, 6-trimethylbenzoylphenylphosphonate.
11. A RATF process polymerization according to claim 5 wherein the chain transfer agent ETPA has the following structure:
12. self-cleaning PETG material according to claim 1, which has excellent self-cleaning function and can be used for various electronic components and optical equipment.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202110072989.7A CN113278181A (en) | 2021-01-20 | 2021-01-20 | Self-cleaning PETG material and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202110072989.7A CN113278181A (en) | 2021-01-20 | 2021-01-20 | Self-cleaning PETG material and application thereof |
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| CN202110072989.7A Withdrawn CN113278181A (en) | 2021-01-20 | 2021-01-20 | Self-cleaning PETG material and application thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115521141A (en) * | 2022-10-19 | 2022-12-27 | 安徽致磨新材料科技有限公司 | Zirconia ceramic wear-resistant micro-bead and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030175488A1 (en) * | 2001-11-30 | 2003-09-18 | General Electric Company | Multilayer articles comprising resorcinol arylate polyester and method for making thereof |
| US20130034689A1 (en) * | 2011-08-05 | 2013-02-07 | Andrew Tye Hunt | Inorganic Nanocoating Primed Organic Film |
| CN103130969A (en) * | 2013-02-06 | 2013-06-05 | 上海维凯化学品有限公司 | Fluoropolymer microsphere |
| US20170198164A1 (en) * | 2014-05-30 | 2017-07-13 | Riken Technos Corporation | Actinic-ray-curable resin composition, layered film including hardcoat formed therefrom, and layered transparent resin product |
-
2021
- 2021-01-20 CN CN202110072989.7A patent/CN113278181A/en not_active Withdrawn
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030175488A1 (en) * | 2001-11-30 | 2003-09-18 | General Electric Company | Multilayer articles comprising resorcinol arylate polyester and method for making thereof |
| US20130034689A1 (en) * | 2011-08-05 | 2013-02-07 | Andrew Tye Hunt | Inorganic Nanocoating Primed Organic Film |
| CN103130969A (en) * | 2013-02-06 | 2013-06-05 | 上海维凯化学品有限公司 | Fluoropolymer microsphere |
| US20170198164A1 (en) * | 2014-05-30 | 2017-07-13 | Riken Technos Corporation | Actinic-ray-curable resin composition, layered film including hardcoat formed therefrom, and layered transparent resin product |
Non-Patent Citations (2)
| Title |
|---|
| ALIYEH GHAMKHARI ET AL.: "Antimicrobial activity evaluation of a novel triblock cationic copolymer (PHEMA-b-PNIPAM-b-PVEAH)", 《JOURNAL OF HUMAN, HEALTH AND HALAL METRICS》 * |
| SARTHIK SAMANTA ET AL.: "Smart Polyacrylate Emulsion Based on a New ABC-Type Triblock Copolymer via RAFT-Mediated Surfactant-Free Miniemulsion Polymerization: Its Multifunctional Properties", 《ACS APPL.MATER.INTERFACES》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115521141A (en) * | 2022-10-19 | 2022-12-27 | 安徽致磨新材料科技有限公司 | Zirconia ceramic wear-resistant micro-bead and preparation method thereof |
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