CN113897016A - Super-weather-resistant functional film and preparation method thereof - Google Patents
Super-weather-resistant functional film and preparation method thereof Download PDFInfo
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- C08J2325/00—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 at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
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- C08J2351/00—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
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- C08J2425/00—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 at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2425/02—Homopolymers or copolymers of hydrocarbons
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- 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
- C08J2433/06—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 only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2433/10—Homopolymers or copolymers of methacrylic acid esters
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- 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
- C08J2451/04—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 grafted on to rubbers
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- C08K3/00—Use of inorganic substances as compounding ingredients
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- C08K3/00—Use of inorganic substances as compounding ingredients
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- C08K3/042—Graphene or derivatives, e.g. graphene oxides
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/132—Phenols containing keto groups, e.g. benzophenones
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- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
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- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3432—Six-membered rings
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- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
Abstract
The invention relates to the technical field of new materials, and particularly discloses an ultra-weather-resistant functional film which is prepared from an ASA composite material, wherein ASA rubber powder, AS particles and PMMA are mixed to prepare the film which has the characteristics of high strength and high weather resistance, a far infrared absorbent is added to enable the film to absorb infrared rays, so that the ultra-weather-resistant functional film has an excellent heat insulation function, and the anti-oxidant is matched with an ultraviolet absorbent to further improve the color change resistance; the invention also provides a preparation method of the super weather-resistant functional film, and the functional film obtained by the preparation method has the characteristics of good uniformity, smooth surface, no air bubble and no peeling besides the advantages.
Description
Technical Field
The invention relates to the technical field of new materials, in particular to an ultra-weather-resistant functional film.
Background
The ASA resin film is also called ASA super-weather-resistant functional film, has lasting and bright color, and has excellent weather resistance, chemical corrosion resistance and self-cleaning property. Can be used in the fields of building materials such as synthetic resin tiles, color steel tiles, decorative plates and the like.
The production process of the ASA resin film mainly comprises extrusion, traction and stretching forming, wherein ASA resin particles are subjected to the working procedures of drying, heating, melting, die forming, tabletting, cooling, film winding and the like to produce a film product with the thickness of 8-15 filaments (80-150 mu m).
The super weather-resistant functional film has the characteristics of super high weather resistance, chemical corrosion resistance, good self-cleaning property, small heat shrinkage and the like; the material can be exposed outdoors for a long time, and can still keep the physical properties of the material stable through erosion of sunlight irradiation (ultraviolet rays, ozone and the like), humidity, rain (acid rain), seawater (salt fog), haze and the like, and the mechanical properties of the material such as bending strength, tensile strength and the like can be kept stable; soaking the raw materials in diluted hydrochloric acid, nitric acid, NaOH alkali and other strong acid and alkali under laboratory conditions, wherein the physical properties of the raw materials are still unchanged; outdoor sand dust, sewage and the like cannot stay on the ASA resin film, the ASA resin film is not easy to adsorb dust and scale, and has a typical lotus leaf effect; when the hot-melt adhesive is used at the temperature of about 80 ℃, the shrinkage rate is within +/-0.5 percent, so that the hot-melt adhesive has a wider hot working range; in addition, the super weather-proof functional film is used as the outer film of the color steel tile, so that the pollution of spray paint to the environment is reduced, and the color steel tile has a good application prospect. However, the super-weather-proof functional film in the prior art has the defect of insufficient heat insulation performance, and under high-intensity illumination, the heat insulation performance cannot be improved enough to resist high external temperature only by the materials such as the color steel tile outer film and the like.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide the super-weather-resistant functional film with excellent heat insulation effect.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides an ultra-weather-resistant functional film which is prepared from an ASA composite material, wherein the ASA composite material is prepared from the following raw materials in parts by weight:
further, the ASA rubber powder is a graft copolymer of acrylate rubber, styrene and acrylonitrile, the weight average molecular weight of the ASA rubber powder is 300,000-800,000, the average particle diameter range is 400-1000nm, the rubber content is 40-60 wt%, the relative density is 1.0-1.07g/cm3, and the melting temperature is 190-220 ℃.
Further, the AS particles are a copolymer of styrene and acrylonitrile, the weight-average molecular weight of the AS particles is 100,000-300,000, the content of acrylonitrile is 20-40 wt%, and the melt index is 5-40g/10 min.
The antioxidant is antioxidant 1010 or antioxidant 168.
Further, the compatilizer is maleic anhydride graft or copolymer or methacrylic acid condensed water glyceride graft or copolymer.
Further, the far infrared absorbent is one or more powder materials of graphene, medical stone, bamboo charcoal and silicon carbide.
Further, the ultraviolet absorbent is ultraviolet absorbent uv-770 or ultraviolet absorbent uv-531.
Further, the PMMA particles are general extrusion grade PMMA particles.
The invention also provides a preparation method of the super weather-resistant functional film, which comprises the following steps:
(1) weighing the components according to the proportion, stirring at low speed, mixing and discharging to prepare the ASA composite material;
(2) and (2) placing the ASA composite material prepared in the step (1) in a double-screw granulator, and heating, drawing, cooling and cutting to form ASA composite particles, wherein the barrel temperature of the double-screw granulator is 220-230 ℃.
(3) And (3) placing the ASA composite particles obtained in the step (2) in a homogenizing chamber, and mixing and drying by using hot air, wherein the temperature of the hot air is 60-70 ℃.
(4) And (3) placing the ASA composite particles in a drying oven at the temperature of 80-100 ℃ for continuously drying for 3-5 hours to obtain the ASA composite particles with the water content below 1 per mill.
(5) And (3) placing the ASA composite particles with the water content of less than 1 per mill into a film extruder for extruding and film drawing to form the super weather-resistant functional film with the thickness of 0.08-0.10 mm.
Further, the low-speed stirring and mixing process in the step (1) comprises the following steps: firstly stirring and mixing ASA rubber powder, AS particles, PMMA particles and a compatilizer at a low speed for 7 minutes, then adding toner, a far infrared absorbent, an ultraviolet absorbent and an antioxidant, continuously stirring and mixing at a low speed for 14 minutes, and then discharging to prepare the ASA composite material.
The invention has the following beneficial effects:
according to the super-weather-resistant functional film, ASA rubber powder, AS particles and PMMA are mixed to prepare the super-weather-resistant functional film, so that the super-weather-resistant functional film has the characteristics of high strength and high weather resistance, and meanwhile, a far infrared absorbent is added to enable the super-weather-resistant functional film to absorb infrared rays, so that the super-weather-resistant functional film has an excellent heat insulation function, and the anti-oxidant is matched with the ultraviolet absorbent to further improve the color change resistance; the invention also provides a preparation method of the super weather-resistant functional film, and the functional film obtained by the preparation method has the characteristics of good uniformity, smooth surface, no air bubble and no peeling besides the advantages.
Detailed Description
The present invention will be further described with reference to specific embodiments so as to clearly understand the technical idea of the present invention.
The invention relates to an ultra-weather-resistant functional film, which is used for covering products such as PVC synthetic resin tiles, PVC plastic-steel sectional materials, sheets, plates, pipes and the like, can be directly heated and adhered to cover the materials, has the characteristics of convenient use and wide application range, and is made of an ASA composite material, in examples 1-5, the raw materials of the ASA composite material are introduced as follows, and the component proportions are shown in Table 1;
the ASA rubber powder is a graft copolymer of acrylate rubber, styrene and acrylonitrile, the weight average molecular weight of the ASA rubber powder is 300,000-800,000, the average particle diameter range is 400-1000nm, the rubber content is 40-60 wt%, the relative density is 1.0-1.07g/cm3, and the melting temperature is 190-220 ℃.
The AS particles are copolymer of styrene and acrylonitrile, the weight-average molecular weight of the AS particles is 100,000-300,000, the content of acrylonitrile is 20-40 wt%, and the melt index is 5-40g/10 min.
The antioxidant is antioxidant 1010 or antioxidant 168, preferably antioxidant 1010, and the antioxidant 1010 is a phenolic antioxidant, is one of excellent antioxidant varieties, has the characteristics of good volatility and extraction resistance, high thermal stability, long lasting effect, no pollution, low non-toxic volatility, good compatibility and the like besides good antioxidant performance, can effectively prevent thermal oxidative degradation of a polymer material in a long-term aging process, and can improve the color change resistance of the polymer material under a high-temperature processing condition, thereby effectively preventing the prepared functional film from changing color due to long-term exposure and use.
The compatilizer is maleic anhydride graft or copolymer or methacrylic acid condensed water glyceride graft or copolymer.
The far infrared absorbent is one or more of graphene, medical stone, bamboo charcoal and silicon carbide, preferably graphene powder, and is used for absorbing infrared rays irradiated on the functional film, so that the functional film has excellent heat-insulating property.
The ultraviolet absorbent is ultraviolet absorbent uv-770 or ultraviolet absorbent uv-531, preferably ultraviolet absorbent uv-770, has good ultraviolet absorption effect, can be used together with antioxidant to improve heat resistance, and can further improve light stabilization effect.
The PMMA particles are general extrusion grade PMMA particles.
The toner selects plastic toner, and toners with different colors can be selected according to market demands so that the functional film can show different colors.
Table 1:
| raw materials | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 |
| ASA rubber powder | 50 | 40 | 45 | 50 | 60 |
| AS particles | 40 | 50 | 45 | 35 | 30 |
| PMMA particles | 5 | 2 | 5 | 10 | 4 |
| Compatilizer | 2 | 5 | 1 | 1.5 | 3 |
| Toner powder | 1.0 | 2.0 | 1.5 | 0.5 | 1.0 |
| Far infrared absorbent | 1.0 | 0.6 | 2.0 | 1.5 | 0.6 |
| Ultraviolet absorber | 0.5 | 0.3 | 0.1 | 0.5 | 1.0 |
| Antioxidant agent | 0.5 | 0.1 | 0.4 | 1.0 | 0.4 |
The invention also discloses a preparation method of the super weather-resistant functional film, taking the super weather-resistant functional film in the embodiment 1 as an example, the preparation method comprises the following steps:
(1) weighing 50 parts of ASA rubber powder, 40 parts of AS particles, 5 parts of PMMA particles, 2 parts of compatilizer, 1 part of toner, 1 part of far infrared absorbent, 0.5 part of ultraviolet absorbent and 0.5 part of antioxidant according to the weight ratio, stirring and mixing the raw materials at low speed for 10-30 minutes, and discharging to prepare a uniform ASA composite material;
(2) and (2) continuously putting the ASA composite material prepared in the step (1) into a double-screw granulator for granulation, wherein ASA composite particles are formed after heating, melting, extruding and drawing into strip materials, cooling with cold water, cutting into granules and processing into granules, wherein the ASA composite particles are cylindrical particles with the diameter of 0.8-1mm and the length of 2-3 mm.
It is worth mentioning that the heating cylinder temperature of the twin-screw granulator is 230 ℃ at 220-.
(3) Placing the ASA composite particles obtained in the step (2) in a homogenizing chamber, and mixing and drying by using hot air, wherein the temperature of the hot air is 60-70 ℃, and preferably 65 ℃; and hot air is fed from bottom to top by utilizing the homogenizing chamber, blades in the homogenizing chamber are used for stirring, so that the uniformity of the material is further improved, and the water carried by the ASA composite particles during cooling and molding is removed by utilizing centrifugal force and the hot air.
(4) And (2) placing the ASA composite particles in a drying oven at the temperature of 80-100 ℃ for continuously drying for 3-5 hours, preferably drying at the temperature of 90 ℃ for 4 hours, and reducing the water content to dryness under the condition of avoiding the water boiling, thereby obtaining the ASA composite particles with the water content of less than 1 per thousand.
(5) The ASA composite particles with the water content of less than 1 per mill are placed in a film extruder to be melted, extruded and drawn to form the super weather-proof functional film with the thickness of 0.08-0.10mm, wherein the barrel temperature of the film extruder is 230-240 ℃, and the preferable temperature is 235 ℃.
Preferably, the low-speed stirring and mixing process in the step (1) is as follows: firstly stirring and mixing ASA rubber powder, AS particles, PMMA particles and a compatilizer at a low speed for 7 minutes, then adding toner, a far infrared absorbent, an ultraviolet absorbent and an antioxidant, continuously stirring and mixing at a low speed for 14 minutes, and then discharging to prepare the ASA composite material.
It is worth mentioning that because of the low-speed stirring, additional cooling equipment is not needed during stirring.
The film is cooled by air cooling or natural cooling, the edge cutting processing can be carried out while the film is cooled, so that a synthesized functional film with the specification and the size is formed, and finally the film is rolled by a rolling machine to form the film roll with the super-weather-proof function.
The preparation method effectively improves the mixing uniformity of the materials in the production process of the functional film, fully removes the water in the materials, and the obtained functional film has the characteristics of good uniformity, smooth surface, no bubbles and no peeling besides the advantages.
And (3) performance testing:
the functional films prepared in the examples and the existing ASA film were subjected to a heat insulation test in which the PVC plastic steel pipes completely covered with the ultra weather-resistant functional films of examples 1 to 5 and the existing ASA film respectively and sealed at both ends were cooled for one day from an environment of 20 ℃ and then taken out to be placed in an outdoor environment and exposed to the sun, and the temperature inside the PVC plastic steel pipes was periodically measured with a temperature sensor, to obtain the following results of table 2:
| type of coating film | T0 | T1 | T2 | T3 | T4 |
| Existing ASA films | 20℃ | 23.8℃ | 27.7℃ | 29.4℃ | 30.8℃ |
| Example 1 | 20℃ | 21.8℃ | 22.4℃ | 24.3℃ | 26.0℃ |
| Example 2 | 20℃ | 21.9℃ | 22.9℃ | 25.0℃ | 26.8℃ |
| Example 3 | 20℃ | 22.3℃ | 22.7℃ | 24.8℃ | 26.5℃ |
| Example 4 | 20℃ | 22.0℃ | 23.0℃ | 25.5℃ | 27.0℃ |
| Example 5 | 20℃ | 21.7℃ | 22.7℃ | 24.9℃ | 26.6℃ |
| Ambient temperature | / | 36.3℃ | 36.5℃ | 34.7℃ | 32.3℃ |
From the results of table 2, it can be seen that the ultra weatherable functional films of examples 1-5 of the present invention all had significantly higher thermal insulation properties than the prior art ASA films.
Various other changes and modifications to the above-described embodiments and concepts will become apparent to those skilled in the art from the above description, and all such changes and modifications are intended to be included within the scope of the present invention as defined in the appended claims.
Claims (10)
1. The super-weather-resistant functional film is characterized by being prepared from an ASA composite material, wherein the ASA composite material is prepared from the following raw materials in parts by weight:
2. the ultra weatherable functional film according to claim 1, wherein the ASA rubber powder is a graft copolymer of acrylate rubber with styrene and acrylonitrile.
3. The ultra-weatherable functional film according to claim 1, wherein the AS particles are a copolymer of styrene and acrylonitrile.
4. The ultra-weatherable functional film according to claim 1, wherein the antioxidant is antioxidant 1010 or antioxidant 168.
5. The ultra-weatherable functional film according to claim 1, wherein the compatibilizer is a maleic anhydride graft or copolymer or a methacrylic acid condensed water glyceride graft or copolymer.
6. The film of claim 1, wherein the far infrared absorber is one or more of graphene, medical stone, bamboo charcoal and silicon carbide.
7. The super weatherable functional film according to claim 1, wherein the uv absorber is uv absorber uv-770 or uv absorber uv-531.
8. The weatherable functional film according to claim 1, wherein said PMMA particles are general extrusion grade PMMA particles.
9. A method for preparing the ultra weatherable functional film according to any one of claims 1 to 8, comprising the steps of:
(1) weighing the components according to the proportion, stirring at low speed, mixing and discharging to prepare the ASA composite material;
(2) placing the ASA composite material prepared in the step (1) in a double-screw granulator, and heating, bracing, cooling and cutting the ASA composite material to form ASA composite particles, wherein the barrel temperature of the double-screw granulator is 220-230 ℃;
(3) placing the ASA composite particles obtained in the step (2) in a homogenizing chamber, and mixing and drying by using hot air, wherein the temperature of the hot air is 60-70 ℃;
(4) placing the ASA composite particles in a drying oven at the temperature of 80-100 ℃ for continuously drying for 3-5 hours to obtain ASA composite particles with the water content below 1 per mill;
(5) and (3) placing the ASA composite particles with the water content of less than 1 per mill into a film extruder for extruding and film drawing to form the super weather-resistant functional film with the thickness of 0.08-0.10 mm.
10. The method for preparing the ultra-weatherable functional film according to claim 9, wherein the low-speed stirring and mixing process in the step (1) is as follows: firstly stirring and mixing ASA rubber powder, AS particles, PMMA particles and a compatilizer at a low speed for 7 minutes, then adding toner, a far infrared absorbent, an ultraviolet absorbent and an antioxidant, continuously stirring and mixing at a low speed for 14 minutes, and then discharging to prepare the ASA composite material.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116239811A (en) * | 2023-03-03 | 2023-06-09 | 长沙荣思达科技有限公司 | Outdoor high weather-resistant functional film and preparation method thereof |
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