Green and environment-friendly decorative film and preparation method thereof

Abstract

The invention provides an environment-friendly decorative film and a preparation method thereof, and belongs to the technical field of decorative films. The preparation method comprises the following steps: preparing modified furan polyester resin added with 2, 6-dinaphthalene dicarboxylic acid, maleic anhydride and modified nanospheres, heating, melting, casting to form a film, drying, coating a polyacrylic acid adhesive on the surface, pasting on a building, and carrying out ultraviolet curing to obtain the green and environment-friendly decorative film. The modified nanospheres are TiO2 / SiO2 microspheres coated with calcium oxide, and the surfaces of the TiO2 / SiO2 microspheres are modified by a silane coupling agent with sulfydryl to obtain the nanospheres. The prepared green and environment-friendly decorative film has good adhesion, enhanced mechanical properties, good heat resistance, improved melting point and glass-transition temperature, improved thermal decomposition temperature, obviously improved thermal stability, good aging resistance and antibacterial performance, prolonged service life, no formaldehyde release, and no pollution to the environment. And the method has a certain degradation effect on formaldehyde, is green and environment-friendly, and has a wide application prospect.

Description

Technical Field

[0001] The present invention relates to the technical field of decorative films, and particularly relates to a green and environment-friendly decorative film and a preparation method thereof. Background Art

[0002] Formaldehyde is a colorless gas with a special pungent odor, highly toxic and carcinogenic, with a release period of up to 8 - 15 years. It is more harmful to the human body, especially to people with low immunity such as the elderly, children and pregnant women, and is on the list of priority-controlled toxic chemicals in China. Formaldehyde is the most main, widespread and harmful pollutant in indoor air. At present, with the enhancement of the world's environmental protection awareness, people's requirements for the content of volatile organic compounds (VOCs) harmful to the human body, especially the content of formaldehyde, released into the air are becoming more and more strict.

[0003] Indoor formaldehyde mainly comes from some indoor decoration materials, including plywood, particleboard and decorative film paper, etc. Since adhesives (such as urea-formaldehyde resins and melamine-formaldehyde resins) prepared with formaldehyde as raw materials are added during the production and decoration processes of such decoration materials, formaldehyde will be continuously released over time during use, thus causing serious indoor environmental pollution and seriously endangering people's physical health, and its release concentration is greatly affected by environmental temperature and humidity.

[0004] The release of formaldehyde in existing decorative film paper mainly comes from the following sources: on the one hand, adhesives need to be used in the impregnation production process. The main components of existing adhesives are urea-formaldehyde resin filling and melamine resin, which contain a large amount of free formaldehyde and are released during the impregnation production process; on the other hand, during the storage and hot pressing use of decorative film paper, since urea-formaldehyde resin is generated under acidic conditions, after the decorative film paper itself contains free moisture and absorbs a certain amount of moisture, some of the cured resins will undergo hydrolysis reactions under such conditions to release formaldehyde, and insufficient curing and poor storage conditions will accelerate the process of this hydrolysis reaction. Therefore, there is an urgent need to develop an environment-friendly decorative film paper without formaldehyde release.

[0005] In recent years, in the preparation process of decorative adhesive films, waterborne polyurethane adhesives have been widely used in the field of decorative adhesive films due to their safe and environmentally friendly properties. For example, Chinese Patent Document CN104804168A discloses a waterborne polyurethane emulsion, its preparation method and application on a wallpaper base film, and the wallpaper base film. The emulsion comprises the following raw materials: polyester polyol, diisocyanate, hydrophilic chain extender, salt-forming agent and water. Although its application on the wallpaper base film has good waterproof and alkali-proof properties, its scratch resistance, corrosion resistance and wear resistance are not good, and there are also certain problems with its flexibility, which brings difficulties to subsequent processes such as cutting. Chinese Patent Document CN105368370A discloses a waterborne polyurethane wallpaper adhesive, which comprises the following raw material components: polyol, polyisocyanate, first chain extender, second chain extender, third chain extender, organic bismuth catalyst, triethylamine, wetting and leveling agent, mildew-proof agent and thickener. It is safe and environmentally friendly and has excellent alkali resistance, but the waterborne polyurethane wallpaper adhesive has strong adhesiveness, and it is very easy to have adhesion problems during subsequent construction. At the same time, its resistance to external scratch and wear is not good.

[0006] Furan-based polyesters are mainly obtained by first carrying out an esterification reaction or transesterification reaction between biomass furandicarboxylic acid (FDCA) or dimethyl furan-2,5-dicarboxylate (DMFD) and a diol, and then carrying out a polycondensation reaction. Because the furan ring has aromatic ring properties, and the furan-based polyester has rigidity similar to that of terephthalic acid (PTA)-based polyester, the glass transition temperature and melting point of the furan-based polyester are also not much different from those of the PTA-based polyester. The interatomic distance between carboxylic acid groups in PTA is The carboxyl carbon atoms show a linear structure, while the interatomic distance between carboxylic acid groups in FDCA is The carbon atom of the carboxyl unit is non-linear, with an angle of 129.40. This non-linear structure and the polarity conferred by the oxygen atom determine that the furan ring of FDCA is more difficult to flip than the benzene ring of PTA. All these differences make the furan-based polyester exhibit better macroscopic properties. Compared with PTA-based polyester, the furan-based polyester shows better performance in thermomechanical properties, barrier properties and anti-ultraviolet properties. Moreover, the furan-based polyester also has two important advantages: First, different from the raw materials of PTA-based polyester that rely on fossil resources, the raw materials of furan-based polyester are biomass renewable resources, which have the advantages of rich content and wide sources. Therefore, replacing PTA-based polyester with furan-based polyester can alleviate the problem of the increasingly depleted fossil resources; Second, different from PTA-based polyester materials, the commonly used furan-based polyesters at present, such as ethylene glycol furan-2,5-dicarboxylate (PEF) and butylene glycol furan-2,5-dicarboxylate (PBF), are all biodegradable materials, and their mechanical properties, thermal properties and gas barrier properties are better than those of biodegradable materials such as polylactic acid (PLA), polyglycolic acid (PGA), polyhydroxyalkanoates (PHA), etc. However, the poor heat resistance, slow crystallization rate and insufficient toughness of furan-based polyester materials limit their applications. Summary of the Invention

[0007] The object of the present invention is to provide a green and environment-friendly decorative film and a preparation method thereof, which has good adhesion, enhanced mechanical properties, excellent heat resistance, increased melting point and glass transition temperature, increased thermal decomposition temperature, significantly improved thermal stability, good anti-aging and antibacterial properties of the decorative film, extended service life, no formaldehyde release, and certain degradation effect on formaldehyde, is green and environment-friendly, and has broad application prospects.

[0008] The technical solution of the present invention is realized as follows:

[0009] The present invention provides a preparation method of a green and environment-friendly decorative film. The preparation method adds 2,6-naphthalenedicarboxylic acid, maleic anhydride, and a furan polyester resin modified by modified nano-spheres, heats and melts them to form a film by casting, and after drying, coats a polyacrylic acid adhesive on the surface, pastes it on a building, and cures it by ultraviolet light to obtain the green and environment-friendly decorative film; the modified nano-spheres are TiO2 / SiO2 microspheres coated with calcium oxide and are nano-spheres obtained by modifying the surface with a mercapto-containing silane coupling agent.

[0010] As a further improvement of the present invention, it includes the following steps:

[0011] S1. Mix dimethyl furan-2,5-dicarboxylate, 2,6-naphthalenedicarboxylic acid, maleic anhydride, modified nano-spheres, and pentaerythritol, add a catalyst, and under the protection of an inert gas, heat and stir to react, and raise the temperature to remove the unreacted raw materials;

[0012] S2. Subject the product in step S1 to vacuum heating for prepolymerization, raise the temperature for polycondensation, precipitate it in ethanol, filter, wash, and dry to obtain the polymer.

[0013] S3. Heat the polymer to melting, cast it into a film on a clean glass plate, after drying, coat the surface with polyacrylic acid adhesive, and stick it on the building, then cure it with ultraviolet light to obtain the green environmental protection decorative film.

[0014] As a further improvement of the present invention, in step S1, the molar ratio of dimethyl furan - 2,5 - dicarboxylate, 2,6 - dinaphthalenedicarboxylic acid, maleic anhydride, and pentaerythritol is 0.8 - 1:0.1 - 0.2:0.05 - 0.15:1.8 - 2, the addition amount of the modified nanospheres is 10 - 15 wt% of the mass of dimethyl furan - 2,5 - dicarboxylate, the addition amount of the catalyst is 0.1 - 0.5 wt% of the mass of dimethyl furan - 2,5 - dicarboxylate, the catalyst is tetrabutyl titanate, and the conditions for the heating and stirring reaction are to hold the reaction at 175 - 185 °C for 0.5 - 1.5 h, hold the reaction at 185 - 195 °C for 1 - 3 h, and hold the reaction at 195 - 205 °C for 0.5 - 1.5 h.

[0015] As a further improvement of the present invention, the preparation method of the modified nanospheres is as follows:

[0016] T1. Dissolve poly(ethylene 2,5 - furandicarboxylate) in 1,1,2,2 - tetrachloroethane, add calcium hydroxide powder, disperse it evenly by ultrasonic wave, dropwise add ethanol to promote the phase separation of poly(ethylene 2,5 - furandicarboxylate), deposit it on the surface of calcium hydroxide particles to form microcapsules, centrifuge, wash, and dry to obtain calcium hydroxide microcapsules.

[0017] T2. Dissolve tetrabutyl titanate, tetraethyl orthosilicate, and thiol in dichloromethane to obtain an oil phase; add a pore - forming agent, calcium hydroxide microcapsules, and an emulsifier to water, stir and mix evenly to obtain an aqueous suspension; drop the aqueous suspension into the oil phase, adjust the pH value of the solution, emulsify, stir and react, centrifuge, wash, dry, and calcine to obtain TiO₂ / SiO₂ - coated CaO microspheres doped with impurities.

[0018] T3. Add the TiO₂ / SiO₂ - coated CaO microspheres doped with impurities to ethanol, add a silane coupling agent with a mercapto group, heat and stir to react, centrifuge, wash, and dry to obtain the modified nanospheres.

[0019] As a further improvement of the present invention, in step T1, the heating temperature is 120 - 140 °C, and the mass ratio of poly(ethylene 2,5 - furandicarboxylate) to calcium hydroxide powder is 1 - 2:2 - 3.

[0020] As a further improvement of the present invention, the mass ratio of tetrabutyl titanate, tetraethyl orthosilicate, thiol, pore-forming agent, calcium hydroxide microcapsule and emulsifier in step T2 is 3-5:5-8:0.1-0.2:0.5-1:5-7:0.2-0.4, the pH value of the adjusted solution is 10-11, the temperature of the stirring reaction is 50-60 °C, the time is 4-6 h, the temperature of the calcination is 500-600 °C, the time is 1-3 h, the pore-forming agent is cetyltrimethylammonium chloride or cetyltrimethylammonium bromide, and the emulsifier is selected from at least one of Tween-20, Tween-40, Tween-60, Tween-80, and Tween-85.

[0021] As a further improvement of the present invention, the mass ratio of the doped TiO2 / SiO2-coated CaO microspheres and the mercapto-containing silane coupling agent in step T3 is 10-15:3-5. The mercapto-containing silane coupling agent is at least one of silane coupling agent KH580, silane coupling agent KH590, and 3-(triethoxysilyl)-1-propanethiol. The temperature of the heating and stirring reaction is 40-50 °C, and the time is 3-5 h.

[0022] As a further improvement of the present invention, the vacuum degree of the vacuum heating pre-polymerization in step S2 is 0.08-0.12 MPa, the temperature is 220-240 °C, the time is 3-5 h, the vacuum degree of the temperature-raising polycondensation is 500-700 Pa, the temperature is 240-260 °C, and the time is 3-5 h.

[0023] As a further improvement of the present invention, the time of the ultraviolet curing in step S3 is 10-20 min.

[0024] The present invention further protects a green environmental protection decorative film prepared by the above preparation method.

[0025] The present invention has the following beneficial effects:

[0026] Introduce a monomer containing a naphthalene ring structure (2,6-naphthalenedicarboxylic acid) into the main chain of the furan polyester, use the rigid group to restrict the movement of the molecular chain, improve the glass transition temperature and melting point, introduce a tert-butyl structural group (pentaerythritol) through the side chain, increase the steric hindrance between molecules, and inhibit the movement of the chain segments. Introduce a crosslinkable group (maleic anhydride) into the polyester chain, and form a three-dimensional network structure through thermal initiation or ultraviolet (UV) curing to improve the heat resistance and dimensional stability. The thermal decomposition temperature of the crosslinked material is significantly increased, and the low-temperature resistance performance is improved synchronously. In addition, by introducing modified nanospheres with hydroxyl groups on the surface into the polyester molecular chain, on the one hand, the hydroxyl groups can participate in the polyester reaction, so that the nanospheres are linked to the molecular chain, and on the other hand, the hydroxyl groups can improve the chain segment rigidity through intermolecular hydrogen bonds to form a "hydrogen bond crosslinking" micro-region, thereby improving the thermal properties of the furan polyester resin.

[0027] The surface of the modified nanospheres prepared by the present invention also contains thiol groups, which can undergo a click reaction with the polyacrylic acid resin adhesive, thereby chemically bonding the green environmentally friendly decorative film and the polyacrylic acid adhesive, thereby greatly improving the adhesion between the green environmentally friendly decorative film and the adhesive, and improving the adhesion of the green environmentally friendly decorative film.

[0028] The modified nanospheres prepared by the present invention contain alkaline calcium oxide, neutralize acidic substances (such as furan carboxylic acid) generated by polyester degradation, delay the thermal aging process, improve the aging resistance of the green environmentally friendly decorative film, and can also be used as a nucleating agent to promote the rapid crystallization of furan polyester resin and refine the grains, thereby improving the crystallinity. In addition, the shell layer is porous sulfur and carbon doped TiO2 and SiO2, and the nanosphere shell layer has good visible light catalytic degradation of formaldehyde, and can improve the mechanical properties of the resin. In addition, by adding the modified nanospheres in the reaction stage, the problem of directly adding the nanospheres to the resin causing agglomeration and reducing the mechanical properties of the resin is avoided.

[0029] The green and environmentally friendly decorative film prepared by the present invention uses furan polyester as the main matrix. Since the furan polyester material contains a furan ring in the monomer, the oxygen atom of the furan ring makes it have good oxygen barrier and easy dyeing properties, so that the prepared decorative film has more brilliant colors, can protect buildings or metal materials from oxygen, and is not prone to oxidation reaction, thereby playing a good protective role.

[0030] The green and environmentally friendly decorative film prepared by the present invention has good adhesion, enhanced mechanical properties, good heat resistance, increased melting point and glass transition temperature, increased thermal decomposition temperature, and significantly improved thermal stability. The decorative film has good aging resistance and antibacterial properties, extends the service life, does not release formaldehyde, and has a certain degradation effect on formaldehyde. It is green and environmentally friendly and has broad application prospects. DETAILED DESCRIPTION

[0031] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0032] Preparation Example 1 Preparation of modified nanospheres

[0033] Here’s how:

[0034] T1. Heat 1 g of poly(ethylene 2,5-furandicarboxylate) to 120 °C, dissolve it in 50 mL of 1,1,2,2-tetrachloroethane, add 2 g of calcium hydroxide powder (1000 mesh), disperse it by ultrasonic wave at 1000 W for 15 min, dropwise add 100 mL of ethanol, phase separation occurs, centrifuge, wash, and dry to obtain calcium hydroxide microcapsules;

[0035] T2. Dissolve 3 g of tetrabutyl titanate, 5 g of tetraethyl orthosilicate, and 0.1 g of ethanethiol in 100 mL of dichloromethane to obtain an oil phase; add 0.5 g of cetyltrimethylammonium chloride, 5 g of calcium hydroxide microcapsules, and 0.2 g of Tween-20 to 50 mL of water, stir and mix for 15 min to obtain a water suspension; drop the water suspension into the oil phase, adjust the pH value of the solution to 10, emulsify at 8000 r / min for 15 min, stir and react at 50 °C for 4 h, centrifuge, wash, dry, and calcine at 500 °C for 1 h to obtain doped TiO2 / SiO2-coated CaO microspheres;

[0036] T3. Add 10 g of doped TiO2 / SiO2-coated CaO microspheres to 200 mL of ethanol, add 3 g of silane coupling agent KH580, heat to 40 °C, stir and react for 3 h, centrifuge, wash, and dry to obtain modified nanospheres.

[0037] Preparation Example 2 Preparation of Modified Nanospheres

[0038] The method is as follows:

[0039] T1. Heat 2 g of poly(ethylene 2,5-furandicarboxylate) to 140 °C, dissolve it in 50 mL of 1,1,2,2-tetrachloroethane, add 4 g of calcium hydroxide powder (1000 mesh), disperse it by ultrasonic wave at 1000 W for 15 min, dropwise add 100 mL of ethanol, phase separation occurs, centrifuge, wash, and dry to obtain calcium hydroxide microcapsules;

[0040] T2. Dissolve 5 g of tetrabutyl titanate, 8 g of tetraethyl orthosilicate, and 0.2 g of ethanethiol in 100 mL of dichloromethane to obtain an oil phase; add 1 g of cetyltrimethylammonium bromide, 7 g of calcium hydroxide microcapsules, and 0.4 g of Tween-40 to 50 mL of water, stir and mix for 15 min to obtain a water suspension; drop the water suspension into the oil phase, adjust the pH value of the solution to 11, emulsify at 8000 r / min for 15 min, stir and react at 60 °C for 6 h, centrifuge, wash, dry, and calcine at 600 °C for 3 h to obtain doped TiO2 / SiO2-coated CaO microspheres;

[0041] T3. Add 15 g of doped TiO2 / SiO2-coated CaO microspheres to 200 mL of ethanol, add 5 g of silane coupling agent KH590, heat to 50 °C, stir and react for 5 h, centrifuge, wash, and dry to obtain modified nanospheres.

[0042] Preparation Example 3: Preparation of Modified Nanospheres

[0043] The method is as follows:

[0044] T1. Heat 1.5 g of poly(ethylene glycol 2,5-furandicarboxylate) to 130 °C, dissolve it in 50 mL of 1,1,2,2-tetrachloroethane, add 3 g of calcium hydroxide powder (1000 mesh), disperse it by ultrasonic wave at 1000 W for 15 min, dropwise add 100 mL of ethanol, phase separation occurs, centrifuge, wash, and dry to obtain calcium hydroxide microcapsules;

[0045] T2. Dissolve 4 g of tetrabutyl titanate, 6 g of tetraethyl orthosilicate, and 0.15 g of ethanethiol in 100 mL of dichloromethane to obtain an oil phase; add 0.7 g of cetyltrimethylammonium bromide, 6 g of calcium hydroxide microcapsules, and 0.3 g of Tween-85 to 50 mL of water, stir and mix for 15 min to obtain a water suspension; drop the water suspension into the oil phase, adjust the pH value of the solution to 10.5, emulsify at 8000 r / min for 15 min, stir and react at 55 °C for 5 h, centrifuge, wash, dry, and calcine at 550 °C for 2 h to obtain TiO2 / SiO2-coated CaO microspheres doped with;

[0046] T3. Add 12 g of TiO2 / SiO2-coated CaO microspheres doped with into 200 mL of ethanol, add 4 g of silane coupling agent KH580, heat to 45 °C, stir and react for 4 h, centrifuge, wash, and dry to obtain modified nanospheres.

[0047] Comparative Preparation Example 1

[0048] Compared with Preparation Example 3, the difference is that calcium hydroxide microcapsules are not added in step T2.

[0049] Specifically as follows:

[0050] T2. Dissolve 4 g of tetrabutyl titanate, 6 g of tetraethyl orthosilicate, and 0.15 g of ethanethiol in 100 mL of dichloromethane to obtain an oil phase; add 0.7 g of cetyltrimethylammonium bromide and 0.3 g of Tween-85 to 50 mL of water, stir and mix for 15 min to obtain a water suspension; drop the water suspension into the oil phase, adjust the pH value of the solution to 10.5, emulsify at 8000 r / min for 15 min, stir and react at 55 °C for 5 h, centrifuge, wash, dry, and calcine at 550 °C for 2 h to obtain TiO2 / SiO2 hollow microspheres doped with.

[0051] Comparative Preparation Example 2

[0052] Compared with Preparation Example 3, the difference is that tetrabutyl titanate is not added in step T2.

[0053] Specifically as follows:

[0054] T2. Dissolve 10 g of tetraethyl orthosilicate and 0.15 g of ethanethiol in 100 mL of dichloromethane to obtain an oil phase; add 0.7 g of cetyltrimethylammonium bromide, 6 g of calcium hydroxide microcapsules and 0.3 g of Tween-85 to 50 mL of water, stir and mix for 15 min to prepare a water suspension; add the water suspension dropwise to the oil phase, adjust the pH value of the solution to 10.5, emulsify at 8000 r / min for 15 min, stir and react at 55 °C for 5 h, centrifuge, wash, dry, and calcine at 550 °C for 2 h to obtain doped SiO2-coated CaO microspheres.

[0055] Comparative Preparation Example 3

[0056] Compared with Preparation Example 3, the difference lies in that tetraethyl orthosilicate was not added in step T2.

[0057] Specifically as follows:

[0058] T2. Dissolve 10 g of tetrabutyl titanate and 0.15 g of ethanethiol in 100 mL of dichloromethane to obtain an oil phase; add 0.7 g of cetyltrimethylammonium bromide, 6 g of calcium hydroxide microcapsules and 0.3 g of Tween-85 to 50 mL of water, stir and mix for 15 min to prepare a water suspension; add the water suspension dropwise to the oil phase, adjust the pH value of the solution to 10.5, emulsify at 8000 r / min for 15 min, stir and react at 55 °C for 5 h, centrifuge, wash, dry, and calcine at 550 °C for 2 h to obtain doped TiO2-coated CaO microspheres.

[0059] Comparative Preparation Example 4

[0060] Compared with Preparation Example 3, the difference lies in that ethanethiol was not added in step T2.

[0061] Specifically as follows:

[0062] T2. Dissolve 4 g of tetrabutyl titanate and 6 g of tetraethyl orthosilicate in 100 mL of dichloromethane to obtain an oil phase; add 0.7 g of cetyltrimethylammonium bromide, 6 g of calcium hydroxide microcapsules and 0.3 g of Tween-85 to 50 mL of water, stir and mix for 15 min to prepare a water suspension; add the water suspension dropwise to the oil phase, adjust the pH value of the solution to 10.5, emulsify at 8000 r / min for 15 min, stir and react at 55 °C for 5 h, centrifuge, wash, dry, and calcine at 550 °C for 2 h to obtain TiO2 / SiO2-coated CaO microspheres.

[0063] Comparative Preparation Example 5

[0064] Compared with Preparation Example 3, the difference lies in that step T3 was not carried out.

[0065] Specifically as follows:

[0066] T1. Heat 1.5 g of poly(ethylene 2,5-furandicarboxylate) to 130 °C, dissolve it in 50 mL of 1,1,2,2-tetrachloroethane, add 3 g of calcium hydroxide powder (1000 mesh), disperse it by ultrasonic wave at 1000 W for 15 min, dropwise add 100 mL of ethanol, phase separation occurs, centrifuge, wash, and dry to obtain calcium hydroxide microcapsules;

[0067] T2. Dissolve 4 g of tetrabutyl titanate, 6 g of tetraethyl orthosilicate, and 0.15 g of ethanethiol in 100 mL of dichloromethane to obtain an oil phase; add 0.7 g of cetyltrimethylammonium bromide, 6 g of calcium hydroxide microcapsules, and 0.3 g of Tween-85 to 50 mL of water, stir and mix for 15 min to obtain a water suspension; drop the water suspension into the oil phase, adjust the pH value of the solution to 10.5, emulsify at 8000 r / min for 15 min, stir and react at 55 °C for 5 h, centrifuge, wash, dry, and calcine at 550 °C for 2 h to obtain doped TiO2 / SiO2-coated CaO microspheres, which are modified nanospheres.

[0068] Example 1

[0069] This example provides a preparation method of a green and environment-friendly decorative film, including the following steps:

[0070] S1. Mix 0.8 mol of dimethyl 2,5-furandicarboxylate, 0.1 mol of 2,6-dinaphthalenedicarboxylic acid, 0.05 mol of maleic anhydride, the modified nanospheres prepared in Preparation Example 1, and 1.8 mol of pentaerythritol. The addition amount of the modified nanospheres is 10 wt% of the mass of dimethyl 2,5-furandicarboxylate. Add tetrabutyl titanate, and the addition amount of tetrabutyl titanate is 0.1 wt% of the mass of dimethyl 2,5-furandicarboxylate. Under nitrogen protection, keep the temperature at 175 °C for 0.5 h, at 185 °C for 1 h, at 195 °C for 0.5 h, and continue to heat up to remove the unreacted pentaerythritol raw material;

[0071] S2. Prepolymerize the product in step S1 under a vacuum of 0.08 MPa and a temperature of 220 °C for 3 h, and then polycondense it under a vacuum of 500 Pa and a temperature of 240 °C for 3 h. Precipitate it in ethanol, filter, wash, and dry to obtain a polymer;

[0072] S3. Heat the polymer to melt, cast it into a film on a clean glass plate, after drying, coat the surface with polyacrylic acid adhesive, stick it on the building, and cure it with ultraviolet light for 10 min to obtain a green and environment-friendly decorative film.

[0073] Example 2

[0074] This example provides a preparation method of a green and environment-friendly decorative film, including the following steps:

[0075] S1. Mix 1 mol of dimethyl furan-2,5-dicarboxylate, 0.2 mol of 2,6-naphthalenedicarboxylic acid, 0.15 mol of maleic anhydride, the modified nanospheres prepared in Preparation Example 2, and 2 mol of pentaerythritol. The addition amount of the modified nanospheres is 15 wt% of the mass of dimethyl furan-2,5-dicarboxylate. Add tetrabutyl titanate, and the addition amount of tetrabutyl titanate is 0.5 wt% of the mass of dimethyl furan-2,5-dicarboxylate. Under nitrogen protection, keep the temperature at 185 °C for 1.5 h, keep the temperature at 195 °C for 3 h, keep the temperature at 205 °C for 1.5 h, and continue to raise the temperature to remove the unreacted pentaerythritol raw material;

[0076] S2. Prepolymerize the product in step S1 under a vacuum of 0.12 MPa and a temperature of 240 °C for 5 h, then polycondense it under a vacuum of 700 Pa and a temperature of 260 °C for 5 h. Precipitate it in ethanol, filter, wash, and dry to obtain a polymer;

[0077] S3. Heat the polymer to melt, cast it into a film on a clean glass plate, dry it, coat the surface with a polyacrylic acid adhesive, and stick it on a building, then cure it with ultraviolet light for 20 min to obtain a green environmental protection decorative film.

[0078] Example 3

[0079] This example provides a method for preparing a green environmental protection decorative film, which includes the following steps:

[0080] S1. Mix 0.9 mol of dimethyl furan-2,5-dicarboxylate, 0.15 mol of 2,6-naphthalenedicarboxylic acid, 0.1 mol of maleic anhydride, the modified nanospheres prepared in Preparation Example 3, and 1.9 mol of pentaerythritol. The addition amount of the modified nanospheres is 12 wt% of the mass of dimethyl furan-2,5-dicarboxylate. Add tetrabutyl titanate, and the addition amount of tetrabutyl titanate is 0.3 wt% of the mass of dimethyl furan-2,5-dicarboxylate. Under nitrogen protection, keep the temperature at 180 °C for 1 h, keep the temperature at 190 °C for 2 h, keep the temperature at 200 °C for 1 h, and continue to raise the temperature to remove the unreacted pentaerythritol raw material;

[0081] S2. Prepolymerize the product in step S1 under a vacuum of 0.1 MPa and a temperature of 230 °C for 4 h, then polycondense it under a vacuum of 600 Pa and a temperature of 250 °C for 4 h. Precipitate it in ethanol, filter, wash, and dry to obtain a polymer;

[0082] S3. Heat the polymer to melt, cast it into a film on a clean glass plate, dry it, coat the surface with a polyacrylic acid adhesive, and stick it on a building, then cure it with ultraviolet light for 15 min to obtain a green environmental protection decorative film.

[0083] Comparative Example 1

[0084] Compared with Example 3, the difference lies in that the modified nanospheres are prepared from Comparative Preparation Example 1.

[0085] Comparative Example 2

[0086] Compared with Example 3, the difference lies in that the modified nanospheres are prepared from Comparative Preparation Example 2.

[0087] Comparative Example 3

[0088] Compared with Example 3, the difference lies in that the modified nanospheres are prepared from Comparative Preparation Example 3.

[0089] Comparative Example 4

[0090] Compared with Example 3, the difference lies in that the modified nanospheres are prepared from Comparative Preparation Example 4.

[0091] Comparative Example 5

[0092] Compared with Example 3, the difference lies in that the modified nanospheres are prepared from Comparative Preparation Example 5.

[0093] Comparative Example 6

[0094] Compared with Example 3, the difference lies in that 2,6-dinaphthalenedicarboxylic acid is not added.

[0095] Specifically as follows:

[0096] S1. Mix 1.05 mol of dimethyl furan-2,5-dicarboxylate, 0.1 mol of maleic anhydride, the modified nanospheres prepared in Preparation Example 3, and 1.9 mol of pentaerythritol. The addition amount of the modified nanospheres is 12 wt% of the mass of dimethyl furan-2,5-dicarboxylate. Add tetrabutyl titanate, and the addition amount of tetrabutyl titanate is 0.3 wt% of the mass of dimethyl furan-2,5-dicarboxylate. Under nitrogen protection, keep the temperature at 180 °C for 1 h, 190 °C for 2 h, 200 °C for 1 h, and continue to raise the temperature to remove the unreacted pentaerythritol raw material.

[0097] Comparative Example 7

[0098] Compared with Example 3, the difference lies in that maleic anhydride is not added.

[0099] Specifically as follows:

[0100] S1. Mix 1 mol of dimethyl furan-2,5-dicarboxylate, 0.15 mol of 2,6-naphthalenedicarboxylic acid, the modified nanospheres prepared in Preparation Example 3, and 1.9 mol of pentaerythritol. The addition amount of the modified nanospheres is 12 wt% of the mass of dimethyl furan-2,5-dicarboxylate. Add tetrabutyl titanate, and the addition amount of tetrabutyl titanate is 0.3 wt% of the mass of dimethyl furan-2,5-dicarboxylate. Under nitrogen protection, keep the temperature at 180 °C for 1 h, 190 °C for 2 h, 200 °C for 1 h, and continue to raise the temperature to remove the unreacted pentaerythritol raw material.

[0101] Comparative Example 8

[0102] Compared with Example 3, the difference is that the modified nanospheres are not added.

[0103] Specifically as follows:

[0104] S1. Mix 0.9 mol of dimethyl furan-2,5-dicarboxylate, 0.15 mol of 2,6-naphthalenedicarboxylic acid, 0.1 mol of maleic anhydride, and 1.9 mol of pentaerythritol. Add tetrabutyl titanate, and the addition amount of tetrabutyl titanate is 0.3 wt% of the mass of dimethyl furan-2,5-dicarboxylate. Under nitrogen protection, keep the temperature at 180 °C for 1 h, 190 °C for 2 h, 200 °C for 1 h, and continue to raise the temperature to remove the unreacted pentaerythritol raw material.

[0105] Comparative Example 9

[0106] Compared with Example 3, the difference is that pentaerythritol is replaced by 1,4-butanediol.

[0107] Specifically as follows:

[0108] S1. Mix 0.9 mol of dimethyl furan-2,5-dicarboxylate, 0.15 mol of 2,6-naphthalenedicarboxylic acid, 0.1 mol of maleic anhydride, the modified nanospheres prepared in Preparation Example 3, and 1.9 mol of 1,4-butanediol. The addition amount of the modified nanospheres is 12 wt% of the mass of dimethyl furan-2,5-dicarboxylate. Add tetrabutyl titanate, and the addition amount of tetrabutyl titanate is 0.3 wt% of the mass of dimethyl furan-2,5-dicarboxylate. Under nitrogen protection, keep the temperature at 180 °C for 1 h, 190 °C for 2 h, 200 °C for 1 h, and continue to raise the temperature to remove the unreacted 1,4-butanediol raw material.

[0109] Test Example 1

[0110] Perform performance tests on the green environmental protection decorative films prepared in Examples 1-3 and Comparative Examples 1-9, and the results are shown in Table 1 and Table 2.

[0111] Tensile property test: The polymer sample was made into a rectangular spline with the specifications of 0.5 mm × 4 mm × 40 mm, and the tensile test was carried out on it using a universal testing machine. The tensile speed was set at 20 mm / min, and each sample was tested 5 times repeatedly, and the average value was taken.

[0112] Table 1

[0113]

[0114]

[0115] Table 2

[0116]

[0117] As can be seen from the above table, the green environmental protection decorative films prepared in Examples 1-3 of the present invention have good comprehensive properties.

[0118] The above are only the preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. A preparation method of a green environmental protection decorative film, characterized in that, Prepare a furan polyester resin modified with 2,6-naphthalenedicarboxylic acid, maleic anhydride, and modified nanospheres. Heat and melt it to form a film by casting. After drying, coat the surface with a polyacrylic adhesive, stick it on a building, and cure it with ultraviolet light to obtain a green and environmentally friendly decorative film; the modified nanospheres are TiO2 / SiO2 microspheres coated with calcium oxide and modified with a silane coupling agent with a mercapto group on the surface.

2. The preparation method according to claim 1, characterized in that, It includes the following steps: S1. Mix dimethyl furan-2,5-dicarboxylate, 2,6-naphthalenedicarboxylic acid, maleic anhydride, modified nanospheres, and pentaerythritol, add a catalyst, and under the protection of an inert gas, heat and stir to react, and raise the temperature to remove unreacted raw materials; S2. Prepolymerize the product in step S1 under reduced pressure and heat, raise the temperature for polycondensation, precipitate it in ethanol, filter, wash, and dry to obtain a polymer; S3. Heat and melt the polymer, cast it into a film on a clean glass plate, after drying, coat the surface with a polyacrylic adhesive, and stick it on a building, and cure it with ultraviolet light to obtain a green and environmentally friendly decorative film.

3. The preparation method according to claim 2, wherein In step S1, the molar ratio of dimethyl furan-2,5-dicarboxylate, 2,6-naphthalenedicarboxylic acid, maleic anhydride, and pentaerythritol is 0.8 - 1:0.1 - 0.2:0.05 - 0.15:1.8 - 2, the addition amount of the modified nanospheres is 10 - 15 wt% of the mass of dimethyl furan-2,5-dicarboxylate, the addition amount of the catalyst is 0.1 - 0.5 wt% of the mass of dimethyl furan-2,5-dicarboxylate, the catalyst is tetrabutyl titanate, and the conditions for the heating and stirring reaction are to keep the temperature at 175 - 185 °C for 0.5 - 1.5 h, keep the temperature at 185 - 195 °C for 1 - 3 h, and keep the temperature at 195 - 205 °C for 0.5 - 1.5 h.

4. The preparation method according to claim 2, characterized in that, The preparation method of the modified nanospheres is as follows: T1. Heat and dissolve poly(ethylene glycol 2,5-furandicarboxylate) in 1,1,2,2-tetrachloroethane, add calcium hydroxide powder, disperse it evenly by ultrasonic wave, dropwise add ethanol, phase separation occurs, centrifuge, wash, and dry to obtain calcium hydroxide microcapsules; T2. Dissolve tetrabutyl titanate, tetraethyl orthosilicate, and mercaptan in dichloromethane to obtain an oil phase; add a pore-forming agent, calcium hydroxide microcapsules, and an emulsifier to water, stir and mix evenly to obtain a water suspension; drop the water suspension into the oil phase, adjust the pH value of the solution, emulsify, stir and react, centrifuge, wash, dry, and calcine to obtain doped TiO2 / SiO2-coated CaO microspheres; T3. Add the doped TiO2 / SiO2-coated CaO microspheres to ethanol, add a silane coupling agent with a mercapto group, heat and stir to react, centrifuge, wash, and dry to obtain modified nanospheres.

5. The preparation method according to claim 4, characterized in that, In step T1, the heating temperature is 120 - 140 °C, and the mass ratio of poly(ethylene glycol 2,5-furandicarboxylate) to calcium hydroxide powder is 1 - 2:2 - 3.

6. The preparation method according to claim 4, characterized in that, In step T2, the mass ratio of tetrabutyl titanate, tetraethyl orthosilicate, thiol, pore-forming agent, calcium hydroxide microcapsule and emulsifier is 3 - 5:5 - 8:0.1 - 0.2:0.5 - 1:5 - 7:0.2 - 0.

4. The pH value of the adjusted solution is 10 - 11. The temperature of the stirring reaction is 50 - 60 °C and the time is 4 - 6 h. The temperature of the calcination is 500 - 600 °C and the time is 1 - 3 h. The pore-forming agent is cetyltrimethylammonium chloride or cetyltrimethylammonium bromide. The emulsifier is selected from at least one of Tween-20, Tween-40, Tween-60, Tween-80, and Tween-85.

7. The preparation method according to claim 4, characterized in that, In step T3, the mass ratio of the doped TiO2 / SiO2-coated CaO microspheres and the mercapto-containing silane coupling agent is 10 - 15:3 - 5. The mercapto-containing silane coupling agent is at least one of silane coupling agent KH580, silane coupling agent KH590, and 3-(triethoxysilyl)-1-propanethiol. The temperature of the heating and stirring reaction is 40 - 50 °C and the time is 3 - 5 h.

8. The preparation method according to claim 2, characterized in that, In step S2, the vacuum degree of the vacuum heating prepolymerization is 0.08 - 0.12 MPa, the temperature is 220 - 240 °C, and the time is 3 - 5 h. The vacuum degree of the temperature-raising polycondensation is 500 - 700 Pa, the temperature is 240 - 260 °C, and the time is 3 - 5 h.

9. The preparation method according to claim 2, wherein In step S3, the time of the ultraviolet curing is 10 - 20 min.

10. A green environmental protection decorative film prepared by the preparation method according to any one of claims 1 - 9.

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