CN113248821A - Special material and film for high-coverage colored ETFE film particles, preparation method and application - Google Patents
Special material and film for high-coverage colored ETFE film particles, preparation method and application Download PDFInfo
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- CN113248821A CN113248821A CN202110524050.XA CN202110524050A CN113248821A CN 113248821 A CN113248821 A CN 113248821A CN 202110524050 A CN202110524050 A CN 202110524050A CN 113248821 A CN113248821 A CN 113248821A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0892—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms containing monomers with other atoms than carbon, hydrogen or oxygen atoms
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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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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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
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/08—Copolymers of ethene
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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
- C08J2433/00—Characterised by the use 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; Derivatives of such polymers
- C08J2433/04—Characterised by the use 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; Derivatives of such polymers esters
- C08J2433/14—Characterised by the use 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; Derivatives of such polymers esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
- C08J2433/16—Homopolymers or copolymers of esters containing halogen atoms
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2251—Oxides; Hydroxides of metals of chromium
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2265—Oxides; Hydroxides of metals of iron
- C08K2003/2272—Ferric oxide (Fe2O3)
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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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
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
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- Polymers & Plastics (AREA)
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Abstract
The invention discloses a special material for high-coverage colored ETFE film particles, a film, a preparation method and application thereof, wherein the special material comprises the following components in parts by mass: 100 parts of ETFE; 10-50 parts of a plasticizer; 1-3 parts of a surface treatment agent; 10-30 parts of a covering agent; 5-20 parts of a coloring agent; 0.5-2 parts of antioxidant. The film prepared by the special material for the ETFE film particles has high covering rate and low light transmittance; when the coverage rate is the same, the cost is reduced by thinning, and the use cost of the raw materials can be further reduced by increasing the content of the transparent particles. The special material for the ETFE film particles prepared by the invention can be used for preparing various colored fluorine films, and the application range of the ETFE film is expanded. The preparation method has low cost and convenient operation, and is convenient for large-scale production.
Description
Technical Field
The invention relates to the field of plastic modification, in particular to a special material and a film for high-coverage colored ETFE film particles, a preparation method and application thereof.
Background
ETFE (ethylene-tetrafluoroethylene copolymer) is an organic fluoroplastic, and it is very difficult to disperse inorganic substances and thus film formation is impossible. The current color ETFE film is high in price, so that the application of the color ETFE film in home decoration or outdoors is limited, and the current ETFE film is poor in coverage rate and cannot effectively cover bottom layer substances.
Patent CN111499964A discloses an ETFE coloring master batch and application thereof, but the application field of the patent is the field of electric wires and cables, the requirements on covering rate and coloring property are low, and the resin plasticizing performance of the ETFE coloring master batch is not suitable for film preparation. The pigment in the formula is used in too large amount, so that the cost is too high, and the application of the pigment in the field of films is limited. The coloring master batch can only be used for coloring, but the covering performance of the master batch is too poor to meet the requirement of high covering.
Disclosure of Invention
The invention aims to provide colored ETFE film particles with high hiding rate.
In order to achieve the purpose, the invention provides a special material for high-coverage colored ETFE film particles, which comprises the following components in parts by mass:
100 parts of ETFE;
25-45 parts of a plasticizer;
1-3 parts of a surface treatment agent;
10-30 parts of a covering agent;
5-20 parts of a coloring agent;
0.5-2 parts of antioxidant;
in the special material for the film particles, the mass percentage of the coloring agent and the covering agent is 5-20 percent.
Preferably, the bulk density of the ETFE is 1-3g/ml, the melt index is 3-40g/10min, and the melting point is 210-250 ℃.
Preferably, the plasticizer is perfluorohexylmethyl polymethacrylate.
Preferably, the surface treatment agent is a fluorine-containing silane coupling agent with molecular weight greater than 300.
Preferably, the colorant is an inorganic pigment having a D90 particle size of < 1000 nm.
Preferably, the covering agent is an inorganic particle with a sheet structure, and the thickness-to-diameter ratio of the inorganic particle is 1: (3-50), and the D90 particle size is less than 1000 nm.
Preferably, the antioxidant comprises one or more of 1, 1, 3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, tris (2, 4-di-tert-butylphenyl) phosphite, N' -di (β -naphthyl) p-phenylenediamine or bis- (3, 4-epoxycyclohexyl) methyladipate.
The invention also provides a preparation method of the special material for the high-coverage colored ETFE film particles, which is used for preparing the special material for the ETFE film particles and comprises the following steps:
step 1, weighing a coloring agent and a surface treating agent, and uniformly mixing;
step 2, weighing the covering agent and the antioxidant, adding the covering agent and the antioxidant into the material prepared in the step 1, and uniformly mixing;
step 3, weighing ethylene-tetrafluoroethylene copolymer ETFE and a plasticizer, adding the materials prepared in the step 2, uniformly mixing, and granulating by adopting a double-screw extrusion granulator; the length-diameter ratio of the screw is 28-40, the compression ratio of the screw is 1.8-2.2, and the extrusion processing temperature is 240-300 ℃.
The invention also provides a high-coverage colored ETFE film which is prepared from the special material for the film particles.
The invention also provides the application of the special material for the film particles, which is used for home decoration or outdoor articles.
The invention has the beneficial effects that:
(1) the film prepared by the special material for the ETFE film particles has high covering rate and low light transmittance; when the coverage rate is the same, the cost is reduced by thinning; meanwhile, the use cost of the raw materials can be properly reduced by increasing the content of the covering agent.
(2) The special material for the ETFE film particles prepared by the invention can be used for preparing various colored fluorine films, and the application range of the ETFE film is expanded.
(3) The preparation method has low cost and convenient operation, and is convenient for large-scale production.
Detailed Description
The technical solutions of the present invention are described clearly and completely below, and it is obvious that the described embodiments are some, not all embodiments of the present invention. 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.
The invention provides a special material for high-coverage colored ETFE film particles, which comprises the following components in parts by mass:
100 parts of ETFE, wherein the ETFE is powdery, so that other additives can be more uniformly dispersed, the bulk density of the ETFE is 1-3g/ml, the melt index is 3-40g/10min, and the melting point is 210-;
10-50 parts of a plasticizer, wherein the plasticizer is polymethyl methacrylate, and the fluorine atom content of a polymerization unit is 9-19. By adding the plasticizer into the ETFE, the inorganic colorant can be uniformly dispersed in the ETFE, so that the light transmittance is reduced, and the color is more bright; the decomposition temperature of the polymethyl methacrylate is higher than 400 ℃, so that the perfluoromethyl methacrylate is suitable for processing high-temperature fluoroplastic, and cannot be decomposed in the processing process; on the other hand, the polymethyl methacrylate contains hydrophilic groups, which are beneficial to the dispersion and distribution of inorganic nanoparticles, and also contains hydrophobic chains, which are beneficial to the combination of the nanoparticles, matrix resin and plasticizer; in addition, the addition of the plasticizer does not obviously influence the release performance of ETFE;
1-3 parts of a surface treating agent, wherein the surface treating agent is a fluorine-containing silane coupling agent, has a molecular weight of more than 300 and is not easy to volatilize at high temperature, and preferably, the surface treating agent is one or more of perfluorodecyl triethoxysilane, perfluorodecyl trimethoxysilane, perfluorooctyl triethoxysilane and perfluorooctyl triethoxysilane;
10-30 parts of covering agent, wherein the covering agent is inorganic particles with a sheet structure and comprises one or more of zinc oxide, silicon dioxide, aluminum oxide, talcum powder, mica and nano montmorillonite, and the thickness-diameter ratio of the covering agent is 1: (3-50), the D90 particle size is less than 1000nm, preferably, the D90 particle size is 300-800 nm; the covering agent is added into the ETFE, so that the covering rate of the special material for the film particles is improved;
5-20 parts of a colorant which is an inorganic pigment and comprises one or more of titanium dioxide, iron oxide red, micaceous iron oxide, zinc chromate, chromium oxide or carbon black, wherein the D90 particle size of the colorant is less than 1000nm, preferably, the D90 particle size is 300-800 nm;
0.5-2 parts of antioxidant, including one or more of 1, 1, 3-tri (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, tri (2, 4-di-tert-butylphenyl) phosphite, N' -di (beta-naphthyl) p-phenylenediamine or bis- (3, 4-epoxycyclohexyl) methyladipate.
The invention also provides a preparation method of the special material for the high-coverage colored ETFE film particles, which comprises the following steps:
step 1, weighing a coloring agent and a surface treating agent, and uniformly mixing;
step 2, weighing the covering agent and the antioxidant, adding the covering agent and the antioxidant into the material prepared in the step 1, and uniformly mixing;
and 3, weighing the ethylene-tetrafluoroethylene copolymer and the plasticizer, adding the ethylene-tetrafluoroethylene copolymer and the plasticizer into the material prepared in the step 2, uniformly mixing, and granulating by using a double-screw extrusion granulator, wherein the length-diameter ratio of a screw is 28-40, the compression ratio of the screw is 1.8-2.2, and the extrusion processing temperature is 240-300 ℃.
The ETFE film prepared by using the special material for the ETFE film particles as a raw material has high covering rate, the light transmittance of a 75-micron film is less than 7 percent (the light transmittance of the film prepared by using the commercially available color master batch is 16 percent), and the light transmittance of other color films is less than 15 percent (the light transmittance of the film prepared by using the commercially available color master batch is 29 percent).
The special material for the ETFE film particles prepared by the invention is used as a raw material to prepare the ETFE film, and the special material can be used as a raw material for preparing home decoration or outdoor products due to high covering rate and low light transmittance.
While the present invention has been described in detail with reference to the preferred embodiments, it should be understood that the above description should not be taken as limiting the invention. Various modifications and alterations to this invention will become apparent to those skilled in the art upon reading the foregoing description. Accordingly, the scope of the invention should be determined from the following claims.
Claims (10)
1. The special material for the high-covering-rate colored ETFE film particles is characterized by comprising the following components in parts by mass:
100 parts of ETFE;
25-45 parts of a plasticizer;
1-3 parts of a surface treatment agent;
10-30 parts of a covering agent;
5-20 parts of a coloring agent;
0.5-2 parts of antioxidant;
in the special material for the film particles, the mass percentage of the coloring agent and the covering agent is 5-20 percent.
2. The special material for ETFE film particles as claimed in claim 1, wherein the bulk density of ETFE is 1-3g/ml, the melt index is 3-40g/10min, and the melting point is 210-250 ℃.
3. The special material for ETFE film particles as claimed in claim 1, wherein the plasticizer is perfluorohexylmethyl polymethacrylate.
4. The special material for ETFE film particles as claimed in claim 1, wherein the surface treatment agent is a fluorine-containing silane coupling agent with molecular weight more than 300.
5. The special material for ETFE film particles as claimed in claim 1, wherein the colorant is an inorganic pigment with D90 particle size less than 1000 nm.
6. The special material for ETFE film particles as claimed in claim 1, wherein the covering agent is inorganic particles with a sheet structure, and the thickness-to-diameter ratio of the covering agent is 1: (3-50), and the D90 particle size is less than 1000 nm.
7. The special material for ETFE film particles as claimed in claim 1, wherein the antioxidant comprises one or more of 1, 1, 3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, tris (2, 4-di-tert-butylphenyl) phosphite, N' -di (β -naphthyl) p-phenylenediamine or bis- (3, 4-epoxycyclohexyl) methyladipate.
8. A method for preparing a high-covering-rate colored ETFE film particle-dedicated material, which is used for preparing the ETFE film particle-dedicated material as claimed in any one of claims 1 to 7, and which comprises the following steps:
step 1, weighing a coloring agent and a surface treating agent, and uniformly mixing;
step 2, weighing the covering agent and the antioxidant, adding the covering agent and the antioxidant into the material prepared in the step 1, and uniformly mixing;
step 3, weighing ethylene-tetrafluoroethylene copolymer ETFE and a plasticizer, adding the materials prepared in the step 2, uniformly mixing, and granulating by adopting a double-screw extrusion granulator; the length-diameter ratio of the screw is 28-40, the compression ratio of the screw is 1.8-2.2, and the extrusion processing temperature is 240-300 ℃.
9. A high hiding rate colored ETFE film characterized by being prepared from the film particle exclusive use material of any one of claims 1 to 7.
10. Use of the particulate material according to any one of claims 1 to 7 in home or outdoor applications.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110524050.XA CN113248821A (en) | 2021-05-13 | 2021-05-13 | Special material and film for high-coverage colored ETFE film particles, preparation method and application |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202110524050.XA CN113248821A (en) | 2021-05-13 | 2021-05-13 | Special material and film for high-coverage colored ETFE film particles, preparation method and application |
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| CN113248821A true CN113248821A (en) | 2021-08-13 |
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| CN202110524050.XA Pending CN113248821A (en) | 2021-05-13 | 2021-05-13 | Special material and film for high-coverage colored ETFE film particles, preparation method and application |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114539659A (en) * | 2022-01-28 | 2022-05-27 | 苏州弘道新材料有限公司 | Fluoroplastic film for packaging white low-temperature-resistant photovoltaic module and synthetic method |
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|---|---|---|---|---|
| CN102066483A (en) * | 2008-06-16 | 2011-05-18 | 旭硝子株式会社 | Fluororesin film |
| CN104607061A (en) * | 2014-12-18 | 2015-05-13 | 东华大学 | A method of preparing a poly(ethene-co-tetrafluoroethene) film |
| CN109192800A (en) * | 2018-07-15 | 2019-01-11 | 浙江歌瑞新材料有限公司 | A kind of fluorine-containing thin-film solar cells cephacoria and its manufacturing process |
| EP3928853A1 (en) * | 2020-06-24 | 2021-12-29 | Sefar AG | Composite membrane and method for producing a composite membrane |
-
2021
- 2021-05-13 CN CN202110524050.XA patent/CN113248821A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102066483A (en) * | 2008-06-16 | 2011-05-18 | 旭硝子株式会社 | Fluororesin film |
| CN104607061A (en) * | 2014-12-18 | 2015-05-13 | 东华大学 | A method of preparing a poly(ethene-co-tetrafluoroethene) film |
| CN109192800A (en) * | 2018-07-15 | 2019-01-11 | 浙江歌瑞新材料有限公司 | A kind of fluorine-containing thin-film solar cells cephacoria and its manufacturing process |
| EP3928853A1 (en) * | 2020-06-24 | 2021-12-29 | Sefar AG | Composite membrane and method for producing a composite membrane |
Non-Patent Citations (1)
| Title |
|---|
| 前景: "《乙烯-四氟乙烯共聚物复合体系的结构与性能研究》", 《中国博士学位论文全文数据库 (工程科技Ⅰ辑)》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114539659A (en) * | 2022-01-28 | 2022-05-27 | 苏州弘道新材料有限公司 | Fluoroplastic film for packaging white low-temperature-resistant photovoltaic module and synthetic method |
| CN114539659B (en) * | 2022-01-28 | 2023-11-28 | 苏州弘道新材料有限公司 | Fluoroplastic film for packaging white low-temperature-resistant photovoltaic module and synthetic method |
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Application publication date: 20210813 |
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