CN103910919B - transparent thermal insulation composition - Google Patents

Abstract

The invention relates to a transparent heat insulation composition, which comprises a thermoplastic resin material and a compound M shown as the following formula (I)_xWO_{3‑ y}A_y(I) Wherein M is an alkali metal element, W is tungsten, O is oxygen, A is halogen, and 0 < x ≦ 1, 0 < y ≦ 0.5.

Description

transparent thermal insulation composition

technical field

The invention relates to a thermal insulation composition, especially a thermal insulation composition with high light transmittance.

Background technique

Generally, heat insulation film products are mostly added with dye, metal or mica, ATO or LaB ₆ , etc. in resin materials. The biggest disadvantage of this type of heat insulation film is that its infrared (IR) barrier performance is not good, so the heat insulation performance is not good; And its weather resistance is not good, and it is easy to fade after long-term sunlight. In addition, thermal insulation products such as silver multi-layer sputtering film have good thermal insulation effect, but the biggest disadvantage is that the silver coating is not stable in the air. In addition, the manufacturing process of these thermal insulation films is complicated and the cost is relatively high.

It is known that heat insulation film products usually cannot have both high light transmittance and high heat insulation. For example, heat insulation film products that add transparent oxide conductive materials such as antimony tin oxide (SnO ₂ :Sb, referred to as ATO) and indium tin oxide (SnO ₂ :In, referred to as ITO), because the transparent oxide conductive material The conductivity is low, so that its plasma wavelength (about 1000 to 2500 nanometers (nm)) is greater than 1000nm. Therefore, when it is added to the heat insulation film material, although the visible light transmittance of the heat insulation film is improved, its infrared barrier rate is often Less than 50%, and has poor thermal insulation performance. Moreover, although the heat-insulation film product with metal added to the resin material has an infrared shielding rate of 50%, its visible light transmittance is only 50%. In addition, the thermal insulation film material added with tungsten oxide doped with alkali metal elements has the problem that the infrared barrier performance is insufficient when the visible light transmittance is increased; and the visible light transmittance decreases when the infrared barrier rate is increased. In addition, if LaB ₆ with a plasma wavelength of 700 to 1100nm is added to the thermal insulation film product, although the thermal insulation film product has a better infrared rejection rate due to its high conductivity, its visible light transmittance is insufficient. . It can be seen that none of the known thermal insulation film products can achieve high transparency and high heat insulation effect at the same time, so it is impossible to provide high-performance thermal insulation film products that meet various application requirements. Therefore, it is still the goal of the industry to develop thermal insulation film materials with high transparency, high thermal insulation performance and high stability to meet the needs of various thermal insulation material applications.

Contents of the invention

According to a specific embodiment, a transparent heat insulating composition is provided, comprising a thermoplastic resin material and a compound represented by the following formula (I):

M _x WO _3-y A _y (I),

Wherein, M is an alkali metal element, W is tungsten, O is oxygen, and A is a halogen, 0<x≦1, 0<y≦0.5. The thermoplastic resin material is selected from polyethylene (Polyethylene, PE), ethylene vinyl acetate (Ethylene Vinyl Acetate, EVA), poly (ethylene-ethylene vinyl acetate), polyvinylidene fluoride (Polyvinylidene fluoride, PVDF), polytetrafluoroethylene ( Polytetrafluoroethene, PTFE), polycarbonate (Polycarbonate, PC), polyvinyl chloride (Polyvinyl chloride, PVC), polypropylene (Polypropylene, PP), polyvinyl alcohol (Polyvinyl Alcohol, PVA), polyester (Polyester) and polystyrene At least one of the group consisting of polyvinylidene chloride (PVDC).

Description of drawings

Fig. 1 is the UV-VIS-IR spectrum according to a specific embodiment;

Figure 2 is a UV-VIS-IR spectrum according to a specific embodiment; and

Figure 3 is a UV-VIS-IR spectrum according to a specific embodiment.

detailed description

The implementation of the present invention is described below through specific examples, and those skilled in the art can understand other advantages and effects of the present invention from the content disclosed in this specification. The present invention can also be implemented or applied through other different specific embodiments, and various modifications and changes can be made to the details in this specification based on different viewpoints and applications without departing from the spirit of this creation.

As used in the specification and claims, the singular forms "a", "an" and "the" include plural referents unless the context dictates otherwise.

The term "or" used in the specification and claims includes the meaning of "and/or" unless otherwise stated in the context.

A transparent heat-insulating composition, comprising a thermoplastic resin material and a compound represented by the following formula (I)

M _x WO _3-y A _y (I),

Wherein, M is an alkali metal element, W is tungsten, O is oxygen, A is a halogen, and 0<x≦1, 0<y≦0.5.

The compound represented by formula (I) is tungsten oxide co-doped with anions and cations. According to a specific embodiment, M is lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs) or a combination thereof. According to a specific embodiment, A is fluorine (F), chlorine (Cl), bromine (Br), iodine (I) or a combination thereof.

In the transparent heat-insulating composition, the amount of the compound represented by formula (I), based on the total weight of the composition, is 0.01wt.% to 10.00wt.%. In a specific embodiment, the amount of the compound represented by formula (I), based on the total weight of the composition, is 0.1wt.% to 10.00wt.%. In a specific embodiment, the amount of the compound represented by formula (I), based on the total weight of the composition, is 0.1wt.% to 5.00wt.%. The amount of the compound represented by formula (I) can vary depending on the desired thickness of the product.

According to a specific embodiment, the compound represented by formula (I) has a plasma wavelength of 800 to 1000 nm. The compound of formula (I) has good conductivity and no absorption in the visible light range, so it can achieve high transparency and high heat insulation effect.

For the preparation of the compound of formula (I), reference may be made to the description in No. TW098143078. It can also be prepared using methods similar to those described in the above patent applications.

Compounds of formula (I) may be in the form of, for example, but not limited to, granules (sometimes referred to herein as powders).

In the transparent heat insulating composition, one or more than one compound of formula (I) may be contained. According to a specific embodiment, the adjustment of the visible and visible light transmittance and the infrared rejection rate requires adjusting the compound of formula (I) (including the type and content, etc.) in the transparent heat-insulating composition. According to a specific embodiment, the amount of the compound represented by formula (I) can be adjusted according to the product thickness of the transparent heat insulating composition.

A transparent heat-insulating composition, comprising a thermoplastic resin material and the compound of the above formula (I).

The thermoplastic resin material of the transparent heat insulating composition may be selected as desired. Examples of thermoplastic resin materials include, but are not limited to: polyethylene, ethylene vinyl acetate, poly(ethylene-ethylene vinyl acetate), polyvinyl difluoride, polytetrafluoroethylene, polycarbonate, polyvinyl chloride, polypropylene, Polyvinyl alcohol, polyester, polyvinyl dichloride and combinations thereof.

According to a specific embodiment, the thermoplastic resin material is selected from polyethylene, ethylene vinyl acetate, poly(ethylene-ethylene vinyl acetate), polyvinyl difluoride, polytetrafluoroethylene, polycarbonate, polyvinyl chloride, polypropylene, Group consisting of polyvinyl alcohol, polyester, polyvinyl dichloride, and combinations thereof.

According to a specific embodiment, the thermoplastic resin material is polyethylene, ethylene vinyl acetate, poly(ethylene-ethylene vinyl acetate), polyvinyl difluoride, polytetrafluoroethylene, polycarbonate, polyvinyl chloride, polypropylene, polypropylene Vinyl alcohol, polyester, polyvinyl dichloride or combinations thereof.

In a specific embodiment, the thermoplastic resin material is polyethylene, ethylene vinyl acetate, poly(ethylene-ethylene vinyl acetate), polyvinyl difluoride, polytetrafluoroethylene, polycarbonate, polyvinyl chloride, polypropylene, polypropylene Vinyl alcohol, polyester, polyvinyl dichloride or mixtures of the above.

In a specific embodiment, the thermoplastic resin material is polyethylene, ethylene vinyl acetate, polyvinyl difluoride, polytetrafluoroethylene, polycarbonate, polyvinyl chloride, polypropylene, polyvinyl dichloride or a mixture thereof.

In some examples of this embodiment, the thermoplastic resin material includes polyethylene. In some examples of this specific embodiment, the thermoplastic resin material includes polyvinyl difluoride. In some examples of this specific embodiment, the thermoplastic resin material includes polytetrafluoroethylene. In some examples of this embodiment, the thermoplastic resin material includes polycarbonate. In some examples of this specific embodiment, the thermoplastic resin material includes polyvinyl chloride. In some examples of this embodiment, the thermoplastic resin material includes polypropylene. In some examples of this specific embodiment, the thermoplastic resin material includes polyvinyl dichloride. In some examples of this specific embodiment, the thermoplastic resin material includes polyethylene and polytetrafluoroethylene.

According to a specific embodiment, polyethylene is used as the thermoplastic resin material of the transparent heat insulating composition. According to a specific embodiment, polyvinyl difluoride is used as the thermoplastic resin material of the transparent heat insulating composition. According to a specific embodiment, polytetrafluoroethylene is used as the thermoplastic resin material of the transparent heat insulating composition. According to a specific embodiment, polycarbonate is used as the thermoplastic resin material of the transparent thermal insulation composition. According to a specific embodiment, polyvinyl chloride is used as the thermoplastic resin material of the transparent heat insulating composition. According to a specific embodiment, polypropylene is used as the thermoplastic resin material of the transparent heat insulating composition. According to a specific embodiment, polyvinyl dichloride is used as the thermoplastic resin material of the transparent heat insulating composition. According to a specific embodiment, a mixture of polyethylene and polytetrafluoroethylene is used as the thermoplastic resin material of the transparent thermal insulation composition.

Transparent thermal insulation composition, can further add compatibilizer (Compatibilizer). According to a specific embodiment, adding a compatibilizer to the transparent heat-insulating composition can make the compatibilizer coat the surface of the compound of formula (I) to produce a surface modification effect, so that in the process of heating, melting and granulation The dispersibility of the compound of formula (I) in the thermoplastic resin material is increased, so that the infrared blocking rate and thermal insulation performance can be effectively increased under the close visible light transmittance.

Examples of compatibilizers include, but are not limited to: ethylene vinyl acetate. The content of the compatibilizer can be adjusted depending on the content of the compound of formula (I). According to a specific embodiment, the weight ratio of the compatibilizer to the compound of formula (I) is 0.01 to 1. In a specific embodiment, the weight ratio of the compatibilizer to the compound of formula (I) is 0.1-1.

According to a specific embodiment, the transparent thermal insulation composition includes a thermoplastic resin material, a compound of formula (I) and a compatibilizer. The thermoplastic resin material is selected from the group consisting of polyethylene, ethylene vinyl acetate, polyvinyl difluoride, polytetrafluoroethylene, polycarbonate, polyvinyl chloride, polypropylene, polyvinyl dichloride, and combinations thereof. The compound of formula (I) is as previously described. The amount of the compound represented by formula (I), based on the total weight of the composition, is 0.01wt.% to 10.00wt.%. In a specific embodiment, the amount of the compound represented by formula (I), based on the total weight of the composition, is 0.1wt.% to 5.00wt.%. Compatibilizers are as described above. A specific embodiment, the weight ratio of the compatibilizer to the compound of formula (I) is 0.01-1. In a specific embodiment, the weight ratio of the compatibilizer to the compound of formula (I) is 0.1-1.

According to a specific embodiment, the transparent thermal insulation composition comprises polyethylene, the compound of formula (I) and ethylene vinyl acetate. In a specific embodiment, the amount of the compound represented by formula (I), based on the total weight of the composition, is 0.1wt.% to 10.00wt.%. In a specific embodiment, the amount of the compound represented by formula (I), based on the total weight of the composition, is 0.1wt.% to 5.00wt.%. In a specific embodiment, the weight ratio of ethylene vinyl acetate to the compound of formula (I) is 0.01-1. In a specific embodiment, the weight ratio of ethylene vinyl acetate to the compound of formula (I) is 0.1-1.

According to a specific embodiment, a transparent heat insulating composition is prepared by mixing the compound represented by the formula (I) with the thermoplastic resin material. According to a specific embodiment, a transparent heat insulating composition is prepared by mixing the compound represented by the formula (I), a compatibilizer and the thermoplastic resin material.

According to a specific embodiment, a transparent heat insulating composition is prepared by dispersing the compound represented by formula (I) in a solvent and mixing it with the thermoplastic resin material. According to a specific embodiment, the transparent heat insulating composition is prepared by grinding and dispersing the compound represented by the formula (I) in a solvent, and mixing it with the thermoplastic resin material. According to a specific embodiment, a transparent heat insulating composition is prepared by dispersing the compound represented by formula (I) in a solvent, adding a compatibilizer, and mixing with the thermoplastic resin material. According to a specific embodiment, a transparent heat insulating composition is prepared by grinding and dispersing the compound represented by formula (I) in a solvent, adding a compatibilizer, and mixing with the thermoplastic resin material. In some examples of these specific embodiments, the preparation of the transparent thermal insulation composition further includes the step of removing the solvent. Examples of solvents include, but are not limited to: water, methanol, ethanol, n-butanol, isopropanol, cyclohexanone, methyl ethyl ketone, methyl tert-butyl ketone, etc., diethyl ether, ethylene glycol dimethyl ether, glycol ether , ethylene glycol ether, tetrahydrofuran (THF), etc., propylene glycol methyl acetate (PGMEA), ethyl-2-ethoxyethanol acetate, 3-ethoxy ethyl propionate, isoamyl acetate, etc., chloroform , n-hexane, heptane, pentane, etc., benzene, toluene, xylene, etc., cyclohexane, etc., and combinations thereof.

Additional additives may optionally be used in the transparent insulating composition. For example, additives that increase the desired physical properties of the thermoplastic resin may be used in the composition. Examples of additives include, but are not limited to: additives for improving the visible light transmittance and/or infrared blocking rate of the transparent heat-insulating composition; anti-aging agents, anti-dripping agents, thermal insulation agents, antioxidants, UV ( Ultraviolet light) absorbers, strength enhancers, etc., and combinations thereof.

According to a specific embodiment, the transparent heat insulating composition is prepared by mixing the compound represented by the formula (I) with the thermoplastic resin material, and heating and melting. According to a specific embodiment, the transparent heat-insulating composition is prepared by mixing the compound represented by the formula (I) with the thermoplastic resin material and granulating. In a specific embodiment, a transparent heat insulating composition is prepared by dispersing the compound represented by formula (I) in a solvent, mixing with the thermoplastic resin material, and granulating. In a specific embodiment, the transparent heat insulating composition is prepared by dispersing the compound represented by the formula (I) in a solvent, mixing with the resin material, and heating and melting. In a specific embodiment, the transparent heat insulating composition is prepared by grinding and dispersing the compound represented by the formula (I) in a solvent, mixing with the thermoplastic resin material, and granulating. In a specific embodiment, the transparent heat insulating composition is prepared by grinding and dispersing the compound represented by the formula (I) in a solvent, mixing with the resin material, and heating and melting. According to a specific embodiment, the transparent thermal insulation composition can be further formed into a film.

According to a specific embodiment, the transparent heat insulating composition is prepared by mixing the compound represented by the formula (I) and the compatibilizer with the thermoplastic resin material, and heating and melting. According to a specific embodiment, the transparent heat-insulating composition is prepared by mixing the compound represented by the formula (I), the compatibilizer and the thermoplastic resin material, and performing granulation. In a specific embodiment, a transparent heat insulating composition is prepared by dispersing the compound represented by formula (I) in a solvent, adding a compatibilizer for pretreatment, mixing with the thermoplastic resin material, and granulating. In a specific embodiment, a transparent heat insulating composition is prepared by dispersing the compound represented by formula (I) in a solvent, adding a compatibilizer for pretreatment, mixing with the resin material, and heating and melting. In a specific embodiment, a transparent heat insulating composition is prepared by grinding and dispersing the compound represented by the formula (I) in a solvent, adding a compatibilizer for pretreatment, mixing with the thermoplastic resin material, and granulating . In a specific embodiment, a transparent heat insulating composition is prepared by grinding and dispersing the compound represented by formula (I) in a solvent, adding a compatibilizer for pretreatment, mixing with the resin material, and heating and melting. According to a specific embodiment, the transparent thermal insulation composition can be further formed into a film.

The preparation of the transparent heat insulating composition can be prepared by the method described later. The detailed preparation method is exemplified in the following examples, and it can also be prepared using a method similar to the examples. It should be understood that the preparation methods and materials used in the examples are only for illustration and are not limited thereto.

The transparent heat-insulating composition can be formed into, for example, but not limited to, the forms of particles, films, plates and films.

According to a specific embodiment, the particles of the transparent thermal insulation composition can be further processed (eg, extruded, sprayed) into a film, or into other forms. The thickness of the film can be optionally adjusted (eg, desired light transmission and thermal barrier properties).

The transparent insulating composition can be used to form an insulating structure comprising one or more films, wherein the film contains the transparent insulating composition. According to a specific embodiment, the thermal insulation structure may contain one or more transparent thermal insulation compositions. According to a specific embodiment, one or more compounds of formula (I) may be contained in the thermal insulation structure. The transparent thermal insulation composition (including type and content, etc.) in the thermal insulation structure can be adjusted according to the requirements of visible light transmittance and infrared blocking rate. The compound of formula (I) (including type and content, etc.) in the heat insulation structure can be adjusted according to the required light transmission and heat insulation properties. The thickness of the film can be adjusted according to the required light transmission and heat insulation properties. According to a specific embodiment, the film containing the transparent thermal insulation composition has a thickness of 1 micrometer (μm) to 5 millimeters (mm). In a specific embodiment, the film containing the transparent thermal insulation composition has a thickness of 1 μm to 3 mm. In a specific embodiment, the film containing the transparent thermal insulation composition has a thickness of 1 μm to 500 μm. Membranes of different thicknesses may be included in the insulation structure. The amount of the compound of formula (I) can be adjusted depending on the film thickness.

The transparent heat insulating composition comprising thermoplastic resin material and above-mentioned compound of formula (I) can be used for any heat insulating material, for example, but not limited to: heat insulating material for agriculture (for example, greenhouse light-transmitting covering material), automobile, building , especially, transparent insulation materials.

The transparent heat-insulating composition comprising a thermoplastic resin material and the above-mentioned compound (I) has the characteristics of high visible light transmittance and high infrared ray blocking rate, and can solve the problem that known heat-insulating materials cannot have both high transparency and high heat-insulating performance defect. In addition, the transparent heat-insulating composition comprising a thermoplastic resin material and the compound (I) above has high stability, which is very suitable for industrial application.

The present invention will be described more specifically by way of examples, but the examples are not intended to limit the scope of the present invention. Unless otherwise specified, "%" and "parts" used in the following examples and comparative examples to express the content of any component and, if any, the amount of any substance are based on weight.

The visible light transmittance and infrared transmittance mentioned in this article are both integral values of (spectral intensity*sunlight intensity distribution) versus wavelength. The calculation range is based on the spectral range set by ISO9050 and the detection limit of the instrument. The calculation range of the visible light transmittance (Tvis) is 380-780nm, and the calculation range of the infrared transmittance is 780-2500nm. Among them, the infrared rejection rate (Rir) =100%-infrared penetration rate, which is the percentage of infrared rays that cannot pass through the transparent heat insulation film.

Example

Comparative example 1

5000 grams (g) of polyethylene (manufactured by Taiwan Polymer Chemicals Co., Ltd.) were directly heated and extruded into a film with a thickness of 100 microns to obtain a transparent PE film. The ultraviolet-visible-infrared (UV-VIS-IR) spectrum was measured, and the results are shown in Table 2 and Figure 1. The thermal insulation performance index (Tvis+Rir)*100 is 101.

Comparative example 2

Get the commercial material of Sekisui Chemical, agricultural heat-shielding film (thickness 110 microns), as shown in Table 1, measure its UV-VIS-IR spectrum, the results are shown in Table 2 and Figure 1, its thermal insulation performance index (Tvis +Rir)*100 is 109.

Comparative example 3

5000g polycarbonate pellets (manufactured by Taiwan Chemical Fiber Co., Ltd.) were directly heated and extruded into a film with a thickness of 3 mm to obtain a transparent PC film. The ultraviolet-visible-infrared (UV-VIS-IR) spectrum was measured, and the results are shown in Table 2 and Figure 3. The thermal insulation performance index (Tvis+Rir)*100 is 108.

Comparative example 4

5000g of polyvinyl difluoride (PVDF) pellets (manufactured by Minnesota Mining Manufacturing Co., Ltd. (3M)) were directly heated and extruded into a film with a thickness of 100 microns to obtain a transparent PVDF film. The ultraviolet-visible-infrared (UV-VIS-IR) spectrum was measured, and the results are shown in Table 2. The heat insulation performance index (Tvis+Rir)*100 was 101.

Example 1

Put 5000g of polyvinyl ester pellets in a container, add anion and cation co-doped tungsten oxide powder Cs _0.33 WO _2.94 Cl _0.02 Br _0.04 while stirring with a stirring motor, wherein the content of the added tungsten oxide powder relative to the total weight of the composition is 1wt.%. , after stirring evenly, heat, melt and granulate to obtain heat-insulating composite resin master batches. The master batch is heated and extruded into a film with a thickness of 100 microns to obtain a polyethylene (PE)/anion and cation co-doped tungsten oxide composite film. The UV-VIS-IR spectrum was measured, and the results are shown in Table 2 and Figure 1. The thermal insulation performance index (Tvis+Rir)*100 was 110.

Example 2

First take 100g of anion and cation co-doped tungsten oxide powder Cs _0.33 WO _2.94 Cl _0.02 Br _0.04 , grind and disperse it in 500 grams (g) of toluene, and perform pretreatment to obtain anion and cation co-doped tungsten oxide toluene solution.

Then take 5000g of polyvinyl ester pellets into the container, and add the above anion and cation co-doped tungsten oxide toluene solution while stirring with a stirring motor, wherein the content of the added tungsten oxide powder is 1wt.% relative to the total weight of the composition. After stirring evenly, the toluene solvent is removed in a vacuum oven, and the remaining mixed ester particles are heated, melted and granulated to obtain heat-insulating composite resin master batches. The master batch is heated and extruded into a film with a thickness of 100 microns to obtain a polyethylene/anion and cation co-doped tungsten oxide composite film. Measure its UV-VIS-IR spectrum, the results are shown in Table 2 and Figure 1 and Figure 2, and its thermal insulation performance index (Tvis+Rir)*100 is 125.

Example 3

First take 100g of anion and cation co-doped tungsten oxide powder Cs _0.33 WO _2.94 Cl _0.02 Br _0.04 , grind and disperse it in 500g of toluene, and add 10% ethylene vinyl acetate relative to the powder content to dissolve it in toluene , carry out pretreatment to obtain anion and cation co-doped tungsten oxide toluene solution.

Then take 5000g of polyvinyl ester pellets in the container, add the above-mentioned ethylene vinyl acetate (EVA) (manufactured by Taiwan Polymer Chemicals Co., Ltd.) and anion and cation co-doped tungsten oxide toluene solution while stirring with a stirring motor, and add The content of tungsten oxide powder is 1wt.% relative to the total weight of the composition. After stirring evenly, the toluene solvent is removed in a vacuum oven, and the remaining mixed ester particles are heated, melted and granulated to obtain heat-insulating composite resin master batches. The masterbatch is heated and extruded into a film with a thickness of 100 microns to obtain a polyethylene/ethylene vinyl acetate/anion and cation co-doped tungsten oxide composite film. The UV-VIS-IR spectrum was measured, and the results are shown in Table 2 and Figure 2. The thermal insulation performance index (Tvis+Rir)*100 was 149.

Example 4

First take 100g of anion and cation co-doped tungsten oxide powder Cs _0.33 WO _2.94 Cl _0.02 Br _0.04 , grind and disperse it in 500g of toluene, and add 20% ethylene vinyl acetate relative to the powder content to dissolve it in toluene , carry out pretreatment to obtain anion and cation co-doped tungsten oxide toluene solution.

Take 5000g of polyvinyl ester pellets in the container, add the above-mentioned ethylene vinyl acetate plus anion and cation co-doped tungsten oxide toluene solution while stirring with a stirring motor, wherein the content of the added tungsten oxide powder relative to the total weight of the composition is 1wt.%. After stirring evenly, the toluene solvent is removed in a vacuum oven, and the remaining mixed ester particles are heated, melted and granulated to obtain heat-insulating composite resin master batches. The masterbatch is heated and extruded into a film with a thickness of 100 microns to obtain a polyethylene/ethylene vinyl acetate/anion and cation co-doped tungsten oxide composite film. The UV-VIS-IR spectrum was measured, and the results are shown in Table 2 and Figure 2. The thermal insulation performance index (Tvis+Rir)*100 was 138.

Example 5

First take 100g of anion and cation co-doped tungsten oxide powder Cs _0.33 WO _2.9 Cl _0.10 , grind and disperse it in 500g of isopropanol for pretreatment to obtain anion and cation co-doped tungsten oxide isopropanol solution.

Then take 5000g polycarbonate pellets (manufactured by Taiwan Chemical Fiber Co., Ltd.) in the container, and add the above-mentioned anion and cation co-doped tungsten oxide isopropanol solution while stirring with a stirring motor, wherein the content of the added tungsten oxide powder is relatively The total weight of the composition is 0.1wt.%. After stirring evenly, the isopropanol solvent is removed in a vacuum oven, and the remaining mixed ester particles are heated, melted and granulated to obtain heat-insulating composite resin master batches. The master batch is heated and extruded into a film with a thickness of 1 mm to obtain a polycarbonate/anion and cation co-doped tungsten oxide composite film. The UV-VIS-IR spectrum was measured, and the results are shown in Table 2 and Figure 3. The thermal insulation performance index (Tvis+Rir)*100 was 144.

Example 6

First take 100g of anion and cation co-doped tungsten oxide powder Cs _0.33 WO _2.9 Cl _0.10 , grind and disperse it in 500g of isopropanol for pretreatment to obtain anion and cation co-doped tungsten oxide isopropanol solution.

Then take 5000g polycarbonate pellets (manufactured by Taiwan Chemical Fiber Co., Ltd.) in the container, and add the above-mentioned anion and cation co-doped tungsten oxide isopropanol solution while stirring with a stirring motor, wherein the content of the added tungsten oxide powder is relatively The total weight of the composition is 0.1wt.%. After stirring evenly, the isopropanol solvent is removed in a vacuum oven, and the remaining mixed ester particles are heated, melted and granulated to obtain heat-insulating composite resin master batches. The master batch is heated and extruded into a film with a thickness of 3 mm to obtain a polycarbonate/anion and cation co-doped tungsten oxide composite film. The UV-VIS-IR spectrum was measured, and the results are shown in Table 2 and Figure 3. The thermal insulation performance index (Tvis+Rir)*100 was 158.

Example 7

First take 100g of anion and cation co-doped tungsten oxide powder Rb _0.33 WO _2.9 Br _0.1 , grind and disperse it in 500g of toluene for pretreatment to obtain anion and cation co-doped tungsten oxide toluene solution.

Then take 5000g of polyvinyl difluoride (PVDF) ester pellets (manufactured by Minnesota Mining Manufacturing Co., Ltd. (3M)) in a container, and add the above-mentioned anion and cation co-doped tungsten oxide toluene solution while stirring with a stirring motor. The content of tungsten powder relative to the total weight of the composition is 1wt.%. After stirring evenly, the toluene solvent is removed in a vacuum oven, and the remaining mixed ester particles are heated, melted and granulated to obtain heat-insulating composite resin master batches. The master batch is heated and extruded into a film with a thickness of 100 microns to obtain a composite film of polyvinyl difluoride (PVDF)/anion and cation co-doped tungsten oxide. The UV-VIS-IR spectrum was measured, and the results are shown in Table 2. The thermal insulation performance index (Tvis+Rir)*100 was 122.

Example 8

First take 100g of anion and cation co-doped tungsten oxide powder K _0.33 WO _2.9 Cl _0.05 Br _0.05 , grind and disperse it in 500g of toluene for pretreatment to obtain anion and cation co-doped tungsten oxide toluene solution.

Take 5000g polypropylene pellets (manufactured by Taiwan Chemical Fiber Co., Ltd.) in the container, add the above-mentioned anion and cation co-doped tungsten oxide toluene solution while stirring with a stirring motor, wherein the content of tungsten oxide powder added is relative to the composition The total weight is 1 wt.%. After stirring evenly, the toluene solvent is removed in a vacuum oven, and the remaining mixed ester particles are heated, melted and granulated to obtain heat-insulating composite resin master batches. The master batch is heated and extruded into a film with a thickness of 100 microns to obtain a composite film of polypropylene/anion and cation co-doped tungsten oxide. The UV-VIS-IR spectrum was measured, and the results are shown in Table 2. The thermal insulation performance index (Tvis+Rir)*100 was 132.

Example 9

First take 100g of anion and cation co-doped tungsten oxide powder K _0.5 WO _2.9 Br _0.1 , grind and disperse it in 500g of toluene for pretreatment to obtain anion and cation co-doped tungsten oxide toluene solution.

Take 5000g polyvinyl chloride pellets (manufactured by Taiwan Plastic Industry Co., Ltd.) in the container, add the above-mentioned anion and cation co-doped tungsten oxide toluene solution while stirring with a stirring motor, wherein the content of the added tungsten oxide powder is relative to the combined The total weight of the substance is 1wt.%. After stirring evenly, the toluene solvent is removed in a vacuum oven, and the remaining mixed ester particles are heated, melted and granulated to obtain heat-insulating composite resin master batches. The master batch is heated and extruded into a film with a thickness of 100 microns to obtain a polyvinyl chloride/anion and cation co-doped tungsten oxide composite film. The UV-VIS-IR spectrum was measured, and the results are shown in Table 2. The thermal insulation performance index (Tvis+Rir)*100 was 142.

Example 10

First take 100g of anion and cation co-doped tungsten oxide powder Na _0.5 WO _2.9 F _0.1 , grind and disperse it in 500g of toluene for pretreatment to obtain anion and cation co-doped tungsten oxide toluene solution.

Take 5000g polyvinyl dichloride (PVDC) ester pellets (manufactured by Taiwan Plastics Industry Co., Ltd.) The content is 1 wt.% relative to the total weight of the composition. After stirring evenly, the toluene solvent is removed in a vacuum oven, and the remaining mixed ester particles are heated, melted and granulated to obtain heat-insulating composite resin master batches. The master batch is heated and extruded into a film with a thickness of 100 microns to obtain a polyvinyl dichloride (PVDC)/anion and cation co-doped tungsten oxide composite film. The UV-VIS-IR spectrum was measured, and the results are shown in Table 2. The thermal insulation performance index (Tvis+Rir)*100 was 122.

Example 11

First take 100g of anion and cation co-doped tungsten oxide powder Na _0.3 Li _0.2 WO _2.9 Cl _0.1 , grind and disperse it in 500g of toluene for pretreatment to obtain anion and cation co-doped tungsten oxide toluene solution.

Then take 2500g of polytetrafluoroethylene ester pellets (manufactured by Muming Enterprise Co., Ltd.) and 2500g of polyvinyl ester pellets (manufactured by Taiwan Polymer Chemicals Co., Ltd.) in a container, stir evenly with a stirring motor, and add the above-mentioned anions and cations while stirring Co-doped tungsten oxide toluene solution, wherein the content of tungsten oxide powder added is 1wt.% relative to the total weight of the composition. After stirring evenly, the toluene solvent is removed in a vacuum oven, and the remaining mixed ester particles are heated, melted and granulated to obtain heat-insulating composite resin master batches. The master batch is heated and extruded into a film with a thickness of 100 microns to obtain a polytetrafluoroethylene/polyethylene/anion-cation co-doped tungsten oxide composite film. The UV-VIS-IR spectrum was measured, and the results are shown in Table 2. The thermal insulation performance index (Tvis+Rir)*100 was 126.

Example 12

First take 500g of anion and cation co-doped tungsten oxide powder Cs _0.33 WO _2.94 Cl _0.02 Br _0.04 , grind and disperse it in 2500g of toluene, and at the same time add 100% ethylene vinyl acetate to the powder content to dissolve it in toluene , carry out pretreatment to obtain anion and cation co-doped tungsten oxide toluene solution.

Take 5000g of polyvinyl ester pellets in the container, add the above-mentioned ethylene vinyl acetate plus anion and cation co-doped tungsten oxide toluene solution while stirring with a stirring motor, wherein the content of the added tungsten oxide powder relative to the total weight of the composition is 5wt.%. After stirring evenly, the toluene solvent is removed in a vacuum oven, and the remaining mixed ester particles are heated, melted and granulated to obtain heat-insulating composite resin master batches. The masterbatch is heated and extruded into a film with a thickness of 20 microns to obtain a polyethylene/ethylene vinyl acetate/anion and cation co-doped tungsten oxide composite film. Its UV-VIS-IR spectrum was measured, and the results are shown in Table 2. Its thermal insulation performance index (Tvis+Rir)*100 was 146.

Table 1

Table 2

As shown in Table 2, compared with Comparative Examples 1 to 4, the products of Examples 1 to 12 containing the compound of formula (I) obviously have higher IR cutoff rate and barrier ratio while having high visible light transmittance. thermal performance index.

Furthermore, the PE products of Examples 1 to 4 and 12 containing the compound of formula (I) have a high visible light transmittance compared with the pure PE of Comparative Example 1 and the product of Comparative Example 2 in which mica and titanium oxide were added to PE. At the same time, it obviously has a higher IR rejection rate and heat insulation performance index. It can be known that the transparent thermal insulation composition containing the compound of formula (I) can provide high thermal insulation performance while having high transparency.

In addition, compared with Example 2, it can be seen from Examples 3, 4 and 12 with the addition of a compatibilizer (EVA), that EVA can be coated on the surface of the nano-insulation powder (compound of formula (I)), and the The powder has the effect of surface modification, which can increase the dispersion of the heat-insulating powder in the resin material during the heating and melting granulation process, so it can effectively increase the infrared rejection rate and insulation performance.

The transparent heat-insulating composition comprising a thermoplastic resin material and the above-mentioned compound (I) has the characteristics of high visible light transmittance and high infrared ray blocking rate, and can solve the problem that known heat-insulating materials cannot have both high transparency and high heat-insulating performance defect. In addition, the transparent heat-insulating composition comprising a thermoplastic resin material and the compound (I) above has high stability, which is very suitable for industrial application.

The above-mentioned examples are only illustrative illustrations of the transparent thermal insulation composition and its preparation, but are not intended to limit the present invention. Any person skilled in the art can modify and change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Therefore, the protection scope of the present invention should be as stated in the claims.

Claims (9)

1. A transparent heat-insulating composition, comprising a thermoplastic resin material and a compound shown in the following formula (I) M _x WO _3-y A _y (I), It is characterized in that M is an alkali metal element, W is tungsten, O is oxygen, and A is halogen, 0<x≦1, 0<y≦0.5; The thermoplastic resin material is at least one selected from the group consisting of polyethylene, ethylene vinyl acetate, polyvinyl chloride, polypropylene, polyvinyl alcohol, and polyvinyl dichloride; and The compatibilizer is coated on the surface of the compound of formula (I), and the weight ratio of the compatibilizer to the compound represented by the formula (I) is 0.01 to 1. 2. The transparent thermal insulation composition of claim 1, wherein the compatibilizer is ethylene vinyl acetate. 3. The transparent heat insulating composition according to claim 2, wherein the thermoplastic resin material is polyethylene. 4. The transparent heat insulating composition according to claim 1, wherein M is at least one selected from the group consisting of lithium, sodium, potassium, rubidium and cesium. 5. The transparent heat insulating composition according to claim 1, wherein A is at least one selected from the group consisting of fluorine, chlorine, bromine and iodine. 6. The transparent heat-insulating composition according to claim 1, characterized in that, the content of the compound represented by the formula (I), based on the total weight of the transparent heat-insulating composition, is 0.01wt.% to 10.00 wt.%. 7. The transparent thermal insulation composition according to claim 1, characterized in that it is in the form of granules, films, plates. 8. The transparent heat insulating composition according to claim 1, characterized in that it is prepared by dispersing the compound represented by the formula (I) in a solvent and mixing it with the thermoplastic resin material. 9. The transparent heat insulating composition as claimed in claim 2, characterized in that, it is prepared by dispersing the compound represented by the formula (I) in a solvent and adding the compatibilizer, and then mixing with the thermoplastic resin material .