CN111605276A - Melt co-extrusion multilayer transparent ultraviolet near-infrared shielding high polymer material, preparation method and application thereof - Google Patents

Melt co-extrusion multilayer transparent ultraviolet near-infrared shielding high polymer material, preparation method and application thereof Download PDF

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CN111605276A
CN111605276A CN202010613885.8A CN202010613885A CN111605276A CN 111605276 A CN111605276 A CN 111605276A CN 202010613885 A CN202010613885 A CN 202010613885A CN 111605276 A CN111605276 A CN 111605276A
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shielding
polymer
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东为富
袁皓
李婷
张旭辉
白绘宇
马丕明
汪洋
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Jiangnan University
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Jiangnan University
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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • C08J2329/00—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 alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
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    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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Abstract

A melting co-extrusion multilayer transparent ultraviolet near-infrared shielding high polymer material, a preparation method and application thereof belong to the technical field of functional composite materials. The structural expression of the material is as follows: A/(TIE/C)n/TIE/B/TIE/(C/TIE)nA; in the formula: a represents a surface layer, B represents a barrier shielding layer, TIE represents an adhesive layer, C represents an additional layer, the materials of A and C are the same or different, and the materials of the surface layers A on two sides are the same or different; A. the material C is thermoplastic high-molecular polymer, and the material of the blocking shielding layer B is thermoplastic high-molecular/CuS-PDA or thermoplastic high-molecular/CuS high-blocking shielding composition. The material can shield ultraviolet light and infrared light, and simultaneously keep higher visible light transmittance. The method has important application in the fields of buildings, automobiles, interior decoration, safety protection, material packaging, energy conservation, emission reduction and the like.

Description

Melt co-extrusion multilayer transparent ultraviolet near-infrared shielding high polymer material, preparation method and application thereof
Technical Field
The invention relates to a melt co-extrusion multilayer transparent ultraviolet near-infrared shielding high polymer material and a preparation method thereof, in particular to application of a multifunctional composite material capable of isolating ultraviolet light and infrared light simultaneously and maintaining high light transmittance, and belongs to the technical field of functional composite materials.
Background
The sunlight is a huge energy body, strong ultraviolet light directly irradiates the earth due to the fact that an ozone layer is damaged, and the ultraviolet light contains large energy due to the fact that the ultraviolet light has high frequency and can damage chemical bonds of organic polymers to enable the organic polymers to age; the ultraviolet light can also fade organic matters in the dye; when ultraviolet light directly irradiates the skin, the ultraviolet light can directly penetrate through the surface layer of the skin of a human body and reach the deep part of the dermis, and the tissue cells of the human body are damaged. Studies have shown that prolonged intense UV irradiation can lead to skin cancer. Therefore, the deep research on the ultraviolet shielding material is significant for scientific research and practical application.
In the solar energy, the ultraviolet light band (290-400nm) is about 5%, the visible light band (400-700nm) is about 43%, and the near infrared light band (700-2500nm) is about 52%. About half of the energy of visible solar radiation comes from near-infrared (700-. With the widespread use of glass windows in modern buildings and vehicles, the utilization rate of air conditioners tends to rise day by day in order to regulate the indoor temperature, thereby causing a great waste of social resources and energy. As is well known, in the situation that the form of energy crisis is becoming more serious, energy conservation has become a major strategy for energy development. The near-infrared shielding material can absorb or reflect most of near-infrared light, can adjust indoor temperature, can save energy and improve environmental comfort, and is widely applied to buildings or traffic glass.
Currently, although there are many uv-shielding and near-ir-shielding composites, these composites have only a single shielding property. The composite material capable of shielding ultraviolet light and infrared light simultaneously is prepared, and higher visible light transmittance is kept.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a melt co-extrusion multilayer transparent ultraviolet near-infrared shielding high polymer material and a preparation method thereof. The material can shield ultraviolet light and infrared light, and simultaneously keep higher visible light transmittance. The method has important application in the fields of buildings, automobiles, interior decoration, safety protection, material packaging, energy conservation, emission reduction and the like.
The technical scheme of the invention is as follows:
a melt co-extrusion multilayer transparent ultraviolet near infrared shielding high molecular material is formed by compounding more than three layers of polymers through a co-extrusion blow molding or co-extrusion casting method, wherein the polymers comprise a resin layer, and the resin layer comprises a surface layer and a blocking shielding layer; the structural expression of the melting co-extrusion multilayer transparent ultraviolet near-infrared shielding high polymer material is as follows: A/(TIE/C)n/TIE/B/TIE/(C/TIE)nA; n is an integer of 0 or more;
in the formula: a represents a surface layer, B represents a barrier shielding layer, TIE represents an adhesive layer, C represents an additional layer, the materials of A and C are the same or different, and the materials of the surface layers A on two sides are the same or different; A. the material C is thermoplastic high-molecular polymer, and the material of the blocking shielding layer B is thermoplastic high-molecular/CuS-PDA or thermoplastic high-molecular/CuS high-blocking shielding composition.
The thermoplastic high molecular polymer is mainly PE, PP, PET, PVC, PVA, PS, PC, ABS, PA-6, PA-66, PU and the like.
The thermoplastic polymer/CuS-PDA or thermoplastic polymer/CuS high-barrier shielding composition is characterized in that the shielding material is prepared by blending the following raw materials:
Figure BDA0002563093500000021
further preferably:
Figure BDA0002563093500000022
the plasticizer is one or more of diglycerol, triglycerol, pentaglycerol, decaglycerol, sorbitol, ethylene glycol, propylene glycol, glycerol, glycidol and polyethylene glycol.
The heat stabilizer is one or more of antioxidant 1010, antioxidant 168, tannic acid, hydroxytyrosol, ellagic acid, chlorogenic acid, caffeic acid, and 6, 7-dihydroxy-4-methylcoumarin.
The metal salt is one or more of magnesium chloride, calcium chloride, zinc chloride, calcium nitrate, calcium sulfate and aluminum chloride.
The ultraviolet near-infrared shielding filler is copper sulfide (CuS) or copper sulfide (CuS-PDA) with melanin coated on the surface.
The shape of the copper sulfide includes granular, flaky, spherical or linear.
The copper sulfide with the surface coated with the melanin is obtained by polymerizing copper sulfide by at least one polymer substance of dopa, dopamine hydrochloride and tyrosine.
The preparation method of the copper sulfide with the surface coated with the melanin comprises the following steps:
a, adding copper sulfide powder into deionized water, and performing ultrasonic dispersion until the mixture is uniform to obtain copper sulfide powder dispersion liquid;
b, adding at least one polymer substance of dopamine, dopamine hydrochloride and tyrosine into the solution, wherein the mass ratio of the copper sulfide powder to the polymer substance is 1: (0.05-1), adjusting the pH value of the solution to 8-10, then reacting at 25-70 ℃ for 3-24 h, centrifuging after the reaction is finished, washing and drying to obtain the copper sulfide coated with melanin.
The preparation method of the thermoplastic polymer/CuS-PDA or thermoplastic polymer/CuS high-barrier shielding composition comprises the following steps: respectively weighing thermoplastic polymer, copper sulfide or copper sulfide (CuS-PDA) with melanin coated on the surface, plasticizer, heat stabilizer and metal salt according to the weight parts, adding into a mixer, and fully and uniformly mixing to obtain a premix; then plasticizing the premix in an oven at 60-120 ℃ for 1-3 hours; and finally, putting the plasticized premix into an extruder, and directly extruding and granulating to prepare the ultraviolet near-infrared shielding thermoplastic polymer shielding material.
The preparation method of the melting co-extrusion multilayer transparent ultraviolet near-infrared shielding high polymer material comprises the following steps: the co-extrusion technology is simultaneous multilayer extrusion molding, that is, several extruders supply different molten material flow separately, two or more kinds of polymer, thermoplastic polymer/CuS-PDA or thermoplastic polymer/CuS high-barrier shielding composition are extruded separately in different extruder heads and compounded in the same die, and each polymer forms resin layer with different properties in the finished film.
The bonding resin is one or the combination of more than two of maleic anhydride grafted polyethylene, surlyn resin, ethylene-vinyl acetate copolymer, ethylene-methyl acrylate copolymer and ethylene-acrylic acid copolymer.
The multilayer transparent ultraviolet near-infrared shielding high polymer material is suitable for the fields of buildings, automobiles, interior decoration, safety protection, material packaging, energy conservation, emission reduction and the like.
The beneficial technical effects of the invention are as follows:
(1) the plasticizer, the heat stabilizer and the metal salt used in the thermoplastic polymer/CuS-PDA or the thermoplastic polymer/CuS resin of the barrier shielding layer are environment-friendly and nontoxic, and can be used in the fields of food, medical barrier shielding packaging materials and the like.
(2) The thermoplastic polymer/CuS-PDA or thermoplastic polymer/CuS resin is used as the barrier shielding layer of the melt extrusion composite film, so that the thickness and cost of the barrier shielding layer of the composite film are reduced, and the phenomenon that the thermoplastic polymer blocks the mouth mold and stops due to cross-linked gel is reduced.
(3) The thermoplastic polymer/CuS-PDA or thermoplastic polymer/CuS combined resin is used as the barrier shielding layer and is co-extruded with other resin, so that the prepared high-barrier shielding film is simple in forming process, industrialization is realized by modifying the existing production device, and large-scale investment caused by the change of a new process is avoided.
(4) The melt co-extrusion multilayer composite high-barrier shielding film barrier shielding layer is low in cost, can effectively shield ultraviolet light and infrared light, keeps higher visible light transmittance, and has excellent heat-insulating property. The method has important application in the fields of buildings, automobiles, interior decoration, safety protection, material packaging, energy conservation, emission reduction and the like.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1:
preparation of ultraviolet near-infrared shielded PET/CuS-PDA or PET/CuS high-barrier shielding composition
Weighing 100 parts by weight of PET (American DuPont, RE15030), 0.1 part by weight of copper sulfide (spherical), 15 parts by weight of sorbitol, 10 parts by weight of diglycerol, 5 parts by weight of tannic acid and 1 part by weight of calcium chloride, adding into a stirrer, and fully and uniformly mixing to obtain a premix; then plasticizing the premix in an oven at 60 ℃ for 3 hours; then, putting the plasticized premix into a single-screw extruder for granulation; thus obtaining PET/CuS barrier shielding layer resin 1.
Example 2:
(1) preparation of polydopamine coated copper sulfide
Firstly, weighing 1 part by weight of copper sulfide (sheet) and adding the copper sulfide (sheet) into 100 parts by weight of deionized water solution, and carrying out ultrasonic treatment in an ice-water bath for 10min to uniformly disperse the copper sulfide; adding 0.2 part by weight of dopamine (alatin) into the solution, adjusting the pH of the solution to 8.5, and then reacting at 50 ℃ for 12 hours; and then centrifuging and washing to obtain clean polydopamine coated copper sulfide.
(2) Preparation of ultraviolet near-infrared shielding PVA/CuS-PDA or PVA/CuS high-barrier shielding composition
Weighing 100 parts by weight of polyvinyl alcohol (China petrochemical great wall energy and chemical industry Ningxia Co., Ltd., trade name 1799), 1 part by weight of polydopamine-coated copper sulfide (sheet), 15 parts by weight of sorbitol, 10 parts by weight of diglycerol, 5 parts by weight of tannic acid and 1 part by weight of calcium chloride, adding into a stirrer, and fully and uniformly mixing to prepare a premix; then plasticizing the premix in an oven at 60 ℃ for 3 hours; then, putting the plasticized premix into a single-screw extruder for granulation; and obtaining PVA/CuS-PDA barrier shielding layer resin 2.
Example 3:
(1) preparation of polydopamine coated copper sulfide
Firstly, weighing 1 part by weight of copper sulfide (linear) and adding the copper sulfide into 100 parts by weight of deionized water solution, and carrying out ultrasonic treatment in an ice-water bath for 10min to uniformly disperse the copper sulfide; adding 0.05 weight part of dopamine hydrochloride (alatin) into the solution, adjusting the pH value of the solution to 8.5, and then reacting for 8 hours at 50 ℃; and then centrifuging and washing to obtain clean polydopamine coated copper sulfide.
(2) Preparation of ultraviolet near-infrared shielding PVA/CuS-PDA or PVA/CuS high-barrier shielding composition
Weighing 100 parts by weight of polyvinyl alcohol (China petrochemical great wall energy and chemical industry Ningxia Co., Ltd., trade name 1799), 4 parts by weight of polydopamine-coated copper sulfide (linear), 15 parts by weight of sorbitol, 10 parts by weight of diglycerol, 5 parts by weight of tannic acid and 1 part by weight of calcium chloride, adding into a stirrer, and fully and uniformly mixing to prepare a premix; then plasticizing the premix in an oven at 60 ℃ for 3 hours; then, putting the plasticized premix into a single-screw extruder for granulation; obtaining PVA/CuS-PDA barrier shielding layer resin 3.
Example 4:
(1) preparation of polydopamine coated copper sulfide
Firstly, weighing 1 part by weight of copper sulfide (spherical) and adding the copper sulfide into 100 parts by weight of deionized water solution, and carrying out ultrasonic treatment in an ice-water bath for 10min to uniformly disperse the copper sulfide; adding 1 weight part of tyrosine (alatin) into the solution, adjusting the pH of the solution to 8.5, and then reacting for 4 hours at 50 ℃; and then centrifuging and washing to obtain clean polydopamine coated copper sulfide.
(2) Preparation of ultraviolet near-infrared shielding PVA/CuS-PDA or PVA/CuS high-barrier shielding composition
Weighing 100 parts by weight of polyvinyl alcohol (China petrochemical great wall energy and chemical industry Ningxia Co., Ltd., trade name 1799), 10 parts by weight of polydopamine-coated copper sulfide (spherical), 15 parts by weight of sorbitol, 10 parts by weight of diglycerol, 5 parts by weight of tannic acid and 1 part by weight of calcium chloride, adding into a stirrer, and fully and uniformly mixing to prepare a premix; then plasticizing the premix in an oven at 60 ℃ for 3 hours; then, putting the plasticized premix into a single-screw extruder for granulation; and obtaining PVA/CuS-PDA barrier shielding layer resin 4.
Example 5:
weighing 100 parts by weight of polyvinyl alcohol (China petrochemical great wall energy and chemical industry Ningxia Co., Ltd., trade name 1799), 1 part by weight of copper sulfide (flake), 15 parts by weight of sorbitol, 10 parts by weight of diglycerol, 5 parts by weight of tannic acid and 1 part by weight of calcium chloride, adding into a stirrer, and fully and uniformly mixing to prepare a premix; then plasticizing the premix in an oven at 60 ℃ for 3 hours; then, putting the plasticized premix into a single-screw extruder for granulation; thus obtaining PVA/CuS barrier shielding layer resin 5.
Example 6:
weighing 100 parts by weight of PET (American DuPont, RE15030), 0.5 part by weight of copper sulfide (spherical), 15 parts by weight of sorbitol, 10 parts by weight of diglycerol, 5 parts by weight of tannic acid and 1 part by weight of calcium chloride, adding into a stirrer, and fully and uniformly mixing to obtain a premix; then plasticizing the premix in an oven at 60 ℃ for 3 hours; then, putting the plasticized premix into a single-screw extruder for granulation; thus obtaining PET/CuS barrier shield layer resin 6.
Example 7:
the structural formula of the composite film is expressed as follows:
PET/TIE/(PET/CuS barrier shield layer resin 1)/TIE/PP,
wherein, PET and PP are surface layers, and PET/CuS barrier shielding layer resin 1 is a barrier shielding layer.
Three extruders are respectively used for supplying different molten material flows, the temperature of a PET machine head is 290 ℃, the temperature of a PET/CuS barrier shielding layer resin 1 machine head is 280 ℃, the temperature of a PP machine head is 210 ℃, and the temperature of a TIE layer maleic anhydride grafted polyethylene machine head is 185 ℃, and the materials are respectively extruded by the different extruder machine heads and then compounded in the same die.
Example 8:
the structural formula of the composite film is expressed as follows:
PA/TIE/PE/TIE/(PVA/CuS-PDA barrier shield layer resin 2)/TIE/PE/TIE/PP,
wherein, PA and PP are surface layers, PE is a secondary inner layer, PVA/CuS-PDA barrier shielding layer resin 2 is a barrier shielding layer, TIE is an adhesive layer, and maleic anhydride grafted polyethylene is used.
Seven extruders are respectively used for supplying different molten material flows, the temperature of a PA machine head is 280 ℃, the temperature of a thermoplastic polymer/CuS-PDA barrier shielding layer resin 2 machine head is 200 ℃, the temperature of a PE machine head is 170 ℃, the temperature of a PP machine head is 210 ℃, the temperature of a TIE layer maleic anhydride grafted polyethylene machine head is 185 ℃, and the materials are respectively extruded by different extruder machine heads and then compounded in the same die.
Comparative example 1:
is a PP film.
The test results of the products obtained in the inventive examples and comparative examples are shown in table 1.
TABLE 1
Item Transmittance of infrared light Transmittance of ultraviolet light Transmittance of visible light
Example 1 75％ 69％ 84％
Example 2 18％ 15％ 65％
Example 3 14％ 13％ 54％
Example 4 10％ 6％ 47％
Example 5 18％ 10％ 67％
Example 6 41％ 35％ 78％
Example 7 14％ 12％ 55％
Example 8 17％ 15％ 64％
Comparative example 1 92％ 88％ 92％
As can be seen from the data in Table 1, compared with examples 1-8, the composite film using the thermoplastic polymer/CuS or thermoplastic polymer/CuS-PDA barrier shielding layer has lower infrared transmittance and ultraviolet transmittance, which indicates that the composite film has excellent ultraviolet and near-infrared shielding performance. From comparison of example 1 with example 6, it can be found that the ultraviolet near-infrared shielding property of the material improves as the content of CuS increases. From example 2, compared with example 5, the transmittance of the melanin-coated CuS in the ultraviolet region is lower, which shows that the ultraviolet shielding performance of the material is improved, but the transmittance of the material in the near infrared region and the visible region is hardly affected. It can be seen from examples 7 and 8 that the multilayer transparent composite film prepared by the melt coextrusion technique has excellent ultraviolet and infrared shielding properties while maintaining acceptable visible light transmission.
Those of ordinary skill in the art will understand that: the invention is not to be considered as limited to the specific embodiments thereof, but is to be understood as being modified in all respects, all changes and equivalents that come within the spirit and scope of the invention.

Claims (9)

1. A melt co-extrusion multilayer transparent ultraviolet near infrared shielding high molecular material is characterized in that the material is formed by compounding more than three layers of polymers through a co-extrusion blow molding or co-extrusion casting method, wherein the polymers comprise a resin layer, and the resin layer comprises a surface layer and a shielding layer; the structural expression of the melting co-extrusion multilayer transparent ultraviolet near-infrared shielding high polymer material is as follows: A/(TIE/C)n/TIE/B/TIE/(C/TIE)nA; n is an integer of 0 or more;
in the formula: a represents a surface layer, B represents a barrier shielding layer, TIE represents an adhesive layer, C represents an additional layer, the materials of A and C are the same or different, and the materials of the surface layers A on two sides are the same or different; A. the material C is thermoplastic high-molecular polymer, and the material of the blocking shielding layer B is thermoplastic high-molecular/CuS-PDA or thermoplastic high-molecular/CuS high-blocking shielding composition.
2. The melt-coextruded multilayer transparent ultraviolet and near-infrared shielding polymer material according to claim 1, wherein: the thermoplastic high molecular polymer is made of PE, PP, PET, PVC, PVA, PS, PC, ABS, PA-6, PA-66 or PU.
3. A melt-coextruded multilayer transparent UV-NIR shielding polymeric material according to claim 2, wherein the thermoplastic polymer/CuS-PDA or thermoplastic polymer/CuS high barrier composition is obtained by blending raw materials comprising:
Figure FDA0002563093490000011
the ultraviolet near-infrared shielding filler is copper sulfide CuS or copper sulfide CuS-PDA with the surface coated with melanin.
4. A melt-coextruded multilayer transparent UV/NIR shielding polymeric material as claimed in claim 3, wherein the thermoplastic polymer/CuS-PDA or thermoplastic polymer/CuS high barrier composition is obtained by blending raw materials comprising:
Figure FDA0002563093490000012
5. the melt-coextruded multilayer transparent ultraviolet and near-infrared shielding polymer material according to claim 3, wherein: the preparation method of the copper sulfide with the surface coated with the melanin comprises the following steps:
a, adding copper sulfide powder into deionized water, and performing ultrasonic dispersion until the mixture is uniform to obtain copper sulfide powder dispersion liquid;
b, adding at least one polymeric substance of dopa, dopamine hydrochloride and tyrosine into the copper sulfide powder dispersion liquid, wherein the mass ratio of copper sulfide powder to the polymeric substance is 1: 0.05-1, adjusting the pH value of the solution to 8-10, reacting at 25-70 ℃ for 3-24 hours, centrifuging after the reaction is finished, washing and drying to obtain the copper sulfide coated with melanin.
6. The melt-coextruded multilayer transparent ultraviolet and near-infrared shielding polymer material according to claim 2, wherein:
the plasticizer is one or more of diglycerol, triglycerol, pentaglycerol, decaglycerol, sorbitol, ethylene glycol, propylene glycol, glycerol, glycidol and polyethylene glycol;
the heat stabilizer is one or more of antioxidant 1010, antioxidant 168, tannic acid, hydroxytyrosol, ellagic acid, chlorogenic acid, caffeic acid, and 6, 7-dihydroxy-4-methylcoumarin;
the metal salt is one or more of magnesium chloride, calcium chloride, zinc chloride, calcium nitrate, calcium sulfate and aluminum chloride.
7. The melt-coextruded multilayer transparent ultraviolet and near-infrared shielding polymer material as claimed in claim 1, wherein the material of the bonding layer is one or a combination of two or more of maleic anhydride grafted polyethylene, surlyn resin, ethylene-vinyl acetate copolymer, ethylene-methyl acrylate copolymer and ethylene-acrylic acid copolymer.
8. A method for preparing a melt co-extrusion multilayer transparent ultraviolet near-infrared shielding high polymer material is characterized by comprising the following steps of:
the co-extrusion technology is simultaneous multilayer extrusion molding, that is, several extruders supply different molten material flow separately, two or more kinds of polymer, thermoplastic polymer/CuS-PDA or thermoplastic polymer/CuS high-barrier shielding composition are extruded separately in different extruder heads and compounded in the same die, and each polymer forms resin layer with different properties separately in the product material.
9. The application of the multilayer transparent ultraviolet near-infrared shielding high polymer material of claims 1-7 is characterized in that: the material is applied to the fields of buildings, automobiles, interior decoration, safety protection, material packaging or energy conservation and emission reduction.
CN202010613885.8A 2020-06-30 2020-06-30 Melt co-extrusion multilayer transparent ultraviolet near-infrared shielding high polymer material, preparation method and application thereof Pending CN111605276A (en)

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