CN114316422A - High-light-transmittance gas film and production method thereof - Google Patents
High-light-transmittance gas film and production method thereof Download PDFInfo
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- CN114316422A CN114316422A CN202210017917.7A CN202210017917A CN114316422A CN 114316422 A CN114316422 A CN 114316422A CN 202210017917 A CN202210017917 A CN 202210017917A CN 114316422 A CN114316422 A CN 114316422A
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- 238000002834 transmittance Methods 0.000 title claims abstract description 68
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 22
- -1 polysiloxane Polymers 0.000 claims abstract description 111
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- 239000004005 microsphere Substances 0.000 claims abstract description 96
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 claims abstract description 44
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 34
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 34
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 30
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000004094 surface-active agent Substances 0.000 claims abstract description 25
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 24
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 24
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 20
- ATGUVEKSASEFFO-UHFFFAOYSA-N p-aminodiphenylamine Chemical compound C1=CC(N)=CC=C1NC1=CC=CC=C1 ATGUVEKSASEFFO-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000005266 casting Methods 0.000 claims abstract description 13
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000007789 gas Substances 0.000 claims description 68
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 38
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- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 16
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
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- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 13
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 13
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims description 12
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- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims description 12
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- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 6
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- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 238000002390 rotary evaporation Methods 0.000 claims description 5
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims description 4
- 125000002252 acyl group Chemical group 0.000 claims description 4
- 238000005660 chlorination reaction Methods 0.000 claims description 4
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 claims description 2
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims 1
- 229940080350 sodium stearate Drugs 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 16
- 230000032683 aging Effects 0.000 abstract description 7
- 239000003795 chemical substances by application Substances 0.000 abstract description 5
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
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- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 3
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- 239000010703 silicon Substances 0.000 description 3
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- 239000004925 Acrylic resin Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
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- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 1
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 1
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- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to the field of gas films, and particularly discloses a high-light-transmittance gas film and a production method thereof. According to the invention, the vinyl polysiloxane microspheres with relatively consistent particle size and good dispersibility are obtained by utilizing acid-base hydrolysis reaction and surfactant regulation. Then, hydroxylating vinyl on the surface of vinyl polysiloxane microspheres by using dilute sulfuric acid, grafting 3-aminopropyltrimethoxysilane on the surface of polysiloxane to obtain 3-aminopropyltrimethoxysilane grafted polysiloxane microspheres, finally grafting N-phenyl-p-phenylenediamine by using succinic acid as a bridging agent to obtain antioxidant polysiloxane microspheres, further adding the prepared antioxidant polysiloxane microspheres into an ethylene-tetrafluoroethylene copolymer, obtaining a master batch by using a double-screw extrusion machine, and casting to form a film to obtain the gas film with high light transmittance and high haze and excellent ageing resistance.
Description
Technical Field
The invention relates to the field of gas films, in particular to a high-light-transmittance gas film and a production method thereof.
Background
The gas-filled membrane has excellent structural characteristics as an important branch of the membrane structure. The inflatable membrane structure has the characteristics of fully utilizing outdoor sunlight and organically combining with surrounding nature while meeting the requirements of building modeling. Modern membrane structures were originally developed as inflatable membrane structures. Wherein the film material has three properties of light weight, plasticity and light transmittance. The light weight of the membrane material brings the possibility of super-large span for the building space of the inflatable membrane structure, the plasticity enables the external form and the internal space of the inflatable membrane structure to have flexible variability, and the light transmission can enable the interface of the inflatable membrane structure to be fuzzified, thereby bringing sufficient natural lighting for the indoor environment. The light space structure of the inflatable membrane structure also conforms to the industry requirements of green and low carbon in the current building industry, has the structural characteristics of large span, quick construction, high light transmission, strong plasticity and the like, can not only build a high-quality space environment, but also reduce the development cost to the maximum extent. And the structural characteristics also make the inflatable membrane structure a new favorite in the field of large-space buildings.
The main material of the inflatable membrane structure is light membrane material, wherein the membrane material used in construction can be mainly divided into two types, one is coating fabric type membrane material, and the other is thermoplastic compound type membrane material. The coated fabric-like films of these two materials are also the most used materials in building construction. Generally, the membrane material of the inflatable membrane structure is composed of a plurality of layers of materials, including a coating layer, a base fabric fiber, a surface layer and the like. In general, the membrane materials are classified into a polyvinyl chloride (PVC) membrane material, an ethylene-tetrafluoroethylene copolymer (ETFE) membrane material and a Polytetrafluoroethylene (PTFE) membrane material, and the mass of the three membrane materials is only 0.05kg/m2-2.0kg/m2Within the range, the weight is extremely light. The PVC membrane material has the characteristics of large elasticity, good flexibility and light weight, so that the membrane material is the membrane material with the widest early application range. However, PVC films also have some drawbacks, and when sunlight is irradiated to PVC films for a long time, the films are gradually aged, and their durability, flexibility and elasticity are deteriorated. However, with the development of the technology, people gradually find out through a plurality of researches and practices that PVDF, PVF and other membrane materials are gradually developed, and the strength and the performance of the membrane materials are obvious due to the materialsThe overall durability of the membrane material is improved, the service life of the membrane material is prolonged from 5 years to about 15 years, the cost of the material is extremely low, and the construction cost of the material can be greatly reduced.
The light transmittance of the film material brings natural lighting capability to the air film building, and compared with the traditional building, the outer enclosure structure of the air film building is made of the film material, so that the air film building is relatively flexible and free in lighting selection, and the mode that light enters the room is diversified. The optical properties of the film materials are mainly reflected in the aspects of light transmittance, reflectivity, absorptivity and the like, so that the film materials have different effects on light, and different film materials have different reflectivities, transmittances and absorptivities. Because the light transmittance of the existing polyvinyl chloride (PVC) film and Polytetrafluoroethylene (PTFE) film is not high, although the light transmittance of the ethylene-tetrafluoroethylene copolymer (ETFE) film is extremely high, reaching 80-95%, the completely transparent property thereof is not good for protecting the privacy of users, and therefore, a film material with high haze and high light transmittance is required to be developed as a novel inflatable film building material.
CN 105085951A discloses a preparation method of a high-light-transmittance high-haze polyester film, which comprises the steps of adding hydroxyl silicone oil into an acrylate reaction system, and fixing organic silicon in a methyl methacrylate system by chemical bonds to obtain a polyester material with both high light transmittance and high haze. The method has the defects that the method is limited to acrylic resin, has large limitation, and cannot be popularized to other film-forming resins, such as polyvinyl chloride, polytetrafluoroethylene and other materials; in addition, the method can only use resin synthesis equipment for integrated molding, so that the transmittance and the haze of the film are inconvenient to adjust according to requirements before use, and the use of the film is influenced.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a high-light-transmittance gas film and a production method thereof.
A production method of a high light transmission gas film comprises the following steps:
(1) adding 8-12 parts of vinyl trimethoxy silane and 1-2 parts of surfactant into 45-55 parts of hydrochloric acid solution with the pH value of 3.8-4.2 at the temperature of 25-35 ℃, stirring at the rotating speed of 300r/min for 4-6min, adding sodium hydroxide aqueous solution with the concentration of 0.1-0.2mol/L to adjust the pH value of 7.5-9, continuously reacting for 4-8h, neutralizing with hydrochloric acid with the concentration of 0.1-0.2mol/L until the pH value of 7, centrifuging to obtain precipitate, washing, drying and crushing to obtain vinyl polysiloxane microspheres;
(2) adding 6-10 parts by mass of the vinyl polysiloxane microspheres prepared in the step (1) into 45-55 parts by mass of dilute sulfuric acid with the concentration of 10-14 wt%, reacting at 65-75 ℃ for 20-40min, centrifuging, taking out precipitates, washing and drying to obtain hydroxyl polysiloxane microspheres;
(3) mixing 6-8 parts by mass of the hydroxyl polysiloxane microspheres prepared in the step (2) with 50-80 parts by mass of xylene, ultrasonically dispersing for 20-40min, adding 4-6 parts by mass of 3-aminopropyltrimethoxysilane, continuously ultrasonically dispersing for 10-30min, then reacting for 2-4h at 70-80 ℃ in a nitrogen atmosphere, cooling to room temperature after the reaction is finished, centrifuging to obtain precipitates, washing and drying to obtain the 3-aminopropyltrimethoxysilane grafted polysiloxane microspheres, wherein the ultrasonic frequency is 40-60kHz, and the power is 100-200W;
(4) mixing 1-2 parts by mass of succinic acid, 1-2 parts by mass of an acylchlorination reagent and 12-16 parts by mass of toluene, stirring and reacting at 65-75 ℃ and at the rotation speed of 100-200r/min for 1-2h, adding 2-4 parts by mass of 3-aminopropyltrimethoxysilane grafted polysiloxane microspheres prepared in the step (3), stirring and reacting at the rotation speed of 100-200r/min for 30-40min at 70-80 ℃, adding 1-2 parts by mass of N-phenyl-p-phenylenediamine, stirring and reacting at the rotation speed of 100-200r/min for 30-40min at 70-80 ℃, removing the toluene at 40-50 ℃ by a rotary evaporation method after the reaction is finished, adding 10-20 parts by mass of methanol, stirring at the rotation speed of 100-200r/min for 1-2min, centrifuging to obtain precipitate, washing and drying to obtain antioxidant polysiloxane microspheres;
(5) according to the mass parts, the ethylene-tetrafluoroethylene copolymer is dried for 4-8h at the temperature of 110-120 ℃ to obtain a dried ethylene-tetrafluoroethylene copolymer; mixing 0.5-1 part of antioxidant polysiloxane microspheres and 90-110 parts of dried ethylene-tetrafluoroethylene copolymer, carrying out melting, mixing, extruding, water cooling and grain cutting by using a double-screw extruder to obtain high-light-transmittance gas film master batch, and then placing the high-light-transmittance gas film master batch into a casting extruder to be melted and extruded into a film, wherein the melt temperature is 310-.
The surfactant is one or a mixture of two or more of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, sodium stearate and disodium ethylene diamine tetraacetate; preferably, the surfactant is prepared from sodium dodecyl benzene sulfonate and disodium ethylene diamine tetraacetate according to the mass ratio of (3-5): (1-2) mixing.
The acyl chlorination reagent is one of thionyl chloride, oxalyl chloride and thionyl chloride.
The temperatures of the first to ninth zones of the double-screw extruder are respectively 295-plus-300 ℃, 300-plus-305 ℃, 305-plus-310 ℃, 310-plus-315 ℃, 315-plus-320 ℃, 320-plus-320 ℃, 315-plus-320 ℃, the head temperature is 300-plus-305 ℃ and the screw rotation speed is 100-plus-200 r/min.
The organic silicon light diffusant with the anti-aging property is prepared and applied to the manufacturing of the air film, the air film with high light transmittance and high haze is obtained, and the anti-aging agent is not added, so that the light transmittance of the air film is prevented from being weakened by the anti-aging agent.
Firstly, vinyl trimethoxy silane monomer is adopted for polymerization to obtain vinyl polysiloxane microspheres. Since the reactivity of the alkoxysilane is high, it is easily subjected to hydrolytic polycondensation under acidic and basic conditions. Under the acidic condition, the silanol is protonated firstly, and as a result of protonation, the charge density of silicon atoms is reduced, and nucleophilic attack is carried out by other silanol more easily. Condensation polymerization under alkaline conditions firstly forms silicon oxygen anions, and then the silicon oxygen anions carry out nucleophilic attack on silanol molecules. Because the vinyltrimethoxysilane monomer is oil-soluble and is heterogeneous when added into water, alkoxy is hydrolyzed by hydrochloric acid, methoxy is converted into silicon hydroxyl, and the water solubility of the vinyltrimethoxysilane monomer is greatly improved. Then, after the pH value of the system is adjusted to be alkaline by adding a sodium hydroxide aqueous solution, the polycondensation reaction of the soluble micromolecules is accelerated, the molecular weight is rapidly increased, and the water solubility is reduced. When the molecular weight and the amount of the soluble small molecules increase to a certain extent, the particles precipitate from the system as primary polysiloxane particles when the critical nucleation concentration is exceeded. However, since the polysiloxane primary particles formed in the reaction process are small in particle size and large in number, the interfacial energy of the system is high, and the system is thermodynamically unstable. As the number of the primary polysiloxane particles increases, the Secondary polysiloxane particles (Secondary particles) are formed by condensation when the critical concentration of Secondary nucleation is exceeded, the interfacial energy is reduced, and the system is stabilized. Since the formation and growth of the secondary particles directly determines the particle size of the final vinylpolysiloxane, it is critical to prepare a monodisperse vinylpolysiloxane that the time of formation of the secondary particles is short, ensuring that each secondary particle undergoes the same process from formation to growth, contributing to the formation of the monodisperse vinylpolysiloxane. Therefore, the invention further adds the surface active agents of sodium dodecyl benzene sulfonate and disodium ethylene diamine tetraacetate in the acidification process, and utilizes the strong chelating ability of sodium ethylene diamine tetraacetate to chelate vinyl silane, thereby enhancing the dispersibility and ensuring the uniformity of the polymerization process; furthermore, because the sodium dodecyl benzene sulfonate is an anionic surfactant, the hydroxyl group obtained by hydrolysis of methoxyl can be activated by the strong electron donating capability of the sodium dodecyl benzene sulfonate, the condensation polymerization reaction is promoted, the reaction time is shortened, and the vinyl polysiloxane microspheres with relatively consistent particle size and better dispersibility are obtained by the synergistic effect of the sodium dodecyl benzene sulfonate and the disodium ethylene diamine tetraacetate.
And further, the invention utilizes the principle that dilute sulfuric acid catalyzes ethylene to produce ethanol, vinyl polysiloxane microspheres are added into dilute sulfuric acid for heating reaction, and vinyl on the surfaces of the vinyl polysiloxane microspheres is alcoholized to obtain hydroxyl polysiloxane. And grafting 3-aminopropyl trimethoxy silane on the surface of polysiloxane by utilizing the principle that methoxy silane is easily substituted by hydroxyl, thereby obtaining the 3-aminopropyl trimethoxy silane grafted polysiloxane microspheres. And finally, using succinic acid as a bridging agent, performing acyl chlorination on two acetic acid groups by using an acyl chlorination reagent, and connecting the 3-aminopropyl trimethoxy silane grafted polysiloxane microspheres and N-phenyl-p-phenylenediamine to obtain the antioxidant polysiloxane microspheres. The antioxidation property of the N-phenyl-p-phenylenediamine is beneficial to preventing the ultraviolet aging and the thermal oxidation aging of the ethylene-tetrafluoroethylene copolymer and prolonging the service life of the gas film. The long organic branched chain on the surface of the polysiloxane microspheres is beneficial to enhancing the dispersibility of the polysiloxane microspheres, and the problems of light transmittance reduction, film mechanical property reduction, fog reduction and the like caused by the agglomeration of the polysiloxane microspheres are prevented.
Finally, the prepared antioxidant polysiloxane microspheres and the ethylene-tetrafluoroethylene copolymer are uniformly mixed through a double-screw extruder to obtain a high-light-transmission gas film master batch, and the high-light-transmission gas film master batch is extruded into a film through a casting extruder to obtain the high-light-transmission gas film.
The high light transmission gas film prepared by the invention can also be used as an anti-counterfeiting film, and the optical anti-counterfeiting film is prepared by adding micro dopants into a liquid material. The anti-counterfeiting label produced by combining the uncopyable optical anti-counterfeiting film with the advanced two-dimensional code has identity uniqueness, high anti-counterfeiting performance and incapability of being imitated, fundamentally solves the problem that products puzzling enterprises for a long time are imitated, saves a large amount of counterfeiting cost, and can rob back the huge market share occupied by the fake products, thereby greatly enhancing the economic benefit of the enterprises.
The invention has the beneficial effects that:
1. according to the invention, the vinyl polysiloxane microspheres with relatively consistent particle size and good dispersibility are obtained by utilizing acid-base hydrolysis reaction and surfactant regulation.
2. According to the invention, vinyl on the surface of vinyl polysiloxane microspheres is hydroxylated by dilute sulfuric acid, 3-aminopropyltrimethoxysilane is grafted on the surface of polysiloxane to obtain 3-aminopropyltrimethoxysilane grafted polysiloxane microspheres, and finally succinic acid is used as a bridging agent to graft N-phenyl-p-phenylenediamine to obtain antioxidant polysiloxane microspheres, so that ultraviolet aging and thermal oxidation aging of an ethylene-tetrafluoroethylene copolymer can be prevented, the service life of a gas film is prolonged, the dispersibility of the gas film is enhanced, and the problems of light transmittance reduction, film mechanical property reduction, fog reduction and the like caused by polysiloxane microsphere agglomeration are prevented.
3. The prepared antioxidant polysiloxane microspheres are further added into an ethylene-tetrafluoroethylene copolymer, a master batch is obtained through a double-screw extruder, and a film is formed through casting, so that the air film with high light transmittance and high haze and excellent ageing resistance is obtained.
Detailed Description
Vinyltrimethoxysilane, cat # s: 1, biological technologies ltd in the west asia.
3-aminopropyltrimethoxysilane, CAS No.: 13822-56-5, cat # s: s24008, Shanghai-derived leaf Biotech Co., Ltd.
N-phenyl-p-phenylenediamine, cat No.: r017985, shanghai yan chemical technology ltd.
Ethylene-tetrafluoroethylene copolymer, cat No.: EP506, Guanguan commercial Plastic materials Ltd.
Example 1
A production method of a high light transmission gas film comprises the following steps:
(1) adding 10 parts by mass of vinyl trimethoxy silane into 50 parts by mass of hydrochloric acid solution with the pH value of 4.0 at the temperature of 30 ℃, stirring at the rotating speed of 200r/min for 5min, adding sodium hydroxide aqueous solution with the concentration of 0.1mol/L to adjust the pH value to 8, continuously reacting for 6h, neutralizing with hydrochloric acid with the concentration of 0.1mol/L to the pH value of 7, centrifuging to obtain precipitate, washing, drying and crushing to obtain vinyl polysiloxane microspheres;
(2) drying the ethylene-tetrafluoroethylene copolymer at 120 ℃ for 6h according to the mass parts to obtain a dried ethylene-tetrafluoroethylene copolymer; mixing 0.8 part of vinyl polysiloxane microspheres and 100 parts of dried ethylene-tetrafluoroethylene copolymer, carrying out melting, mixing, extruding, water cooling and grain cutting by using a double-screw extruder to obtain a high-light-transmittance gas film master batch, and then placing the high-light-transmittance gas film master batch into a casting extruder to melt and extrude the high-light-transmittance gas film master batch into a film, wherein the melt temperature is 320 ℃, the diameter of a primary cooling roll is 1000mm, the temperature of the primary cooling roll is 85 ℃, so that the high-light-transmittance gas film is obtained, and the thickness of the high-light-transmittance gas film is 0.25 mm.
The temperatures of the first zone to the ninth zone of the double-screw extruder are respectively 295 ℃, 300 ℃, 305 ℃, 310 ℃, 315 ℃, 320 ℃ and 315 ℃, the head temperature is 300 ℃ and the screw rotating speed is 150 r/min.
Example 2
A production method of a high light transmission gas film comprises the following steps:
(1) adding 10 parts by mass of vinyl trimethoxy silane and 1 part by mass of surfactant into 50 parts by mass of hydrochloric acid solution with the pH value of 4.0 at the temperature of 30 ℃, stirring at the rotating speed of 200r/min for 5min, adding sodium hydroxide aqueous solution with the concentration of 0.1mol/L to adjust the pH value to 8, continuously reacting for 6h, neutralizing with hydrochloric acid with the concentration of 0.1mol/L to the pH value of 7, centrifuging to obtain precipitate, washing, drying and crushing to obtain vinyl polysiloxane microspheres;
(2) drying the ethylene-tetrafluoroethylene copolymer at 120 ℃ for 6h according to the mass parts to obtain a dried ethylene-tetrafluoroethylene copolymer; mixing 0.8 part of vinyl polysiloxane microspheres and 100 parts of dried ethylene-tetrafluoroethylene copolymer, carrying out melting, mixing, extruding, water cooling and grain cutting by using a double-screw extruder to obtain a high-light-transmittance gas film master batch, and then placing the high-light-transmittance gas film master batch into a casting extruder to melt and extrude the high-light-transmittance gas film master batch into a film, wherein the melt temperature is 320 ℃, the diameter of a primary cooling roll is 1000mm, the temperature of the primary cooling roll is 85 ℃, so that the high-light-transmittance gas film is obtained, and the thickness of the high-light-transmittance gas film is 0.25 mm.
The surfactant is prepared from sodium dodecyl benzene sulfonate and disodium ethylene diamine tetraacetate according to a mass ratio of 4: 1 are mixed.
The temperatures of the first zone to the ninth zone of the double-screw extruder are respectively 295 ℃, 300 ℃, 305 ℃, 310 ℃, 315 ℃, 320 ℃ and 315 ℃, the head temperature is 300 ℃ and the screw rotating speed is 150 r/min.
Example 3
A production method of a high light transmission gas film comprises the following steps:
(1) adding 10 parts by mass of vinyl trimethoxy silane and 1 part by mass of surfactant into 50 parts by mass of hydrochloric acid solution with the pH value of 4.0 at the temperature of 30 ℃, stirring at the rotating speed of 200r/min for 5min, adding sodium hydroxide aqueous solution with the concentration of 0.1mol/L to adjust the pH value to 8, continuously reacting for 6h, neutralizing with hydrochloric acid with the concentration of 0.1mol/L to the pH value of 7, centrifuging to obtain precipitate, washing, drying and crushing to obtain vinyl polysiloxane microspheres;
(2) adding 8 parts by mass of the vinyl polysiloxane microspheres prepared in the step (1) into 50 parts of 12 wt% dilute sulfuric acid, reacting at 70 ℃ for 30min, centrifuging to obtain precipitates, washing and drying to obtain hydroxyl polysiloxane microspheres;
(3) mixing 7 parts by mass of the hydroxyl polysiloxane microspheres prepared in the step (2) with 65 parts by mass of xylene, ultrasonically dispersing for 30min, adding 5 parts by mass of 3-aminopropyltrimethoxysilane, continuously ultrasonically dispersing for 20min, then reacting for 3h at 75 ℃ in a nitrogen atmosphere, cooling to room temperature after the reaction is finished, centrifuging to obtain precipitates, washing and drying to obtain 3-aminopropyltrimethoxysilane grafted polysiloxane microspheres, wherein the ultrasonic frequency is 50kHz, and the power is 160W;
(4) mixing 2 parts by mass of succinic acid, 2 parts by mass of an acylchlorination reagent and 16 parts by mass of toluene, stirring and reacting at 70 ℃ at a rotating speed of 180r/min for 1.5h, adding 3 parts by mass of 3-aminopropyltrimethoxysilane grafted polysiloxane microspheres prepared in the step (3), stirring and reacting at 75 ℃ at a rotating speed of 180r/min for 30min, adding 2 parts by mass of N-phenyl-p-phenylenediamine, stirring and reacting at 75 ℃ at a rotating speed of 180r/min for 30min, removing the toluene at 45 ℃ by a rotary evaporation method after the reaction is finished, adding 15 parts by mass of methanol, stirring at a rotating speed of 180r/min for 1.5min, centrifuging, taking precipitates, washing and drying to obtain antioxidant polysiloxane microspheres;
(5) drying the ethylene-tetrafluoroethylene copolymer at 120 ℃ for 6h according to the mass parts to obtain a dried ethylene-tetrafluoroethylene copolymer; mixing 0.8 part of antioxidant polysiloxane microspheres and 100 parts of dried ethylene-tetrafluoroethylene copolymer, carrying out melting, mixing, extruding, water cooling and grain cutting by using a double-screw extruder to obtain a high-light-transmittance gas film master batch, and then placing the high-light-transmittance gas film master batch into a casting extruder to melt and extrude the high-light-transmittance gas film master batch into a film, wherein the melt temperature is 320 ℃, the diameter of a primary cooling roll is 1000mm, the temperature of the primary cooling roll is 85 ℃, and the high-light-transmittance gas film is obtained and has the thickness of 0.25 mm.
The surfactant is prepared from sodium dodecyl benzene sulfonate and disodium ethylene diamine tetraacetate according to a mass ratio of 4: 1 are mixed.
The acid chloride reagent is thionyl chloride.
The temperatures of the first zone to the ninth zone of the double-screw extruder are respectively 295 ℃, 300 ℃, 305 ℃, 310 ℃, 315 ℃, 320 ℃ and 315 ℃, the head temperature is 300 ℃ and the screw rotating speed is 150 r/min.
Example 4
A production method of a high light transmission gas film comprises the following steps:
(1) adding 10 parts by mass of vinyl trimethoxy silane and 1 part by mass of surfactant into 50 parts by mass of hydrochloric acid solution with the pH value of 4.0 at the temperature of 30 ℃, stirring at the rotating speed of 200r/min for 5min, adding sodium hydroxide aqueous solution with the concentration of 0.1mol/L to adjust the pH value to 8, continuously reacting for 6h, neutralizing with hydrochloric acid with the concentration of 0.1mol/L to the pH value of 7, centrifuging to obtain precipitate, washing, drying and crushing to obtain vinyl polysiloxane microspheres;
(2) adding 8 parts by mass of the vinyl polysiloxane microspheres prepared in the step (1) into 50 parts of 12 wt% dilute sulfuric acid, reacting at 70 ℃ for 30min, centrifuging to obtain precipitates, washing and drying to obtain hydroxyl polysiloxane microspheres;
(3) mixing 7 parts by mass of the hydroxyl polysiloxane microspheres prepared in the step (2) with 65 parts by mass of xylene, ultrasonically dispersing for 30min, adding 5 parts by mass of 3-aminopropyltrimethoxysilane, continuously ultrasonically dispersing for 20min, then reacting for 3h at 75 ℃ in a nitrogen atmosphere, cooling to room temperature after the reaction is finished, centrifuging to obtain precipitates, washing and drying to obtain 3-aminopropyltrimethoxysilane grafted polysiloxane microspheres, wherein the ultrasonic frequency is 50kHz, and the power is 160W;
(4) mixing 2 parts by mass of succinic acid, 2 parts by mass of an acylchlorination reagent and 16 parts by mass of toluene, stirring and reacting at 70 ℃ at a rotating speed of 180r/min for 1.5h, adding 3 parts by mass of 3-aminopropyltrimethoxysilane grafted polysiloxane microspheres prepared in the step (3), stirring and reacting at 75 ℃ at a rotating speed of 180r/min for 30min, adding 2 parts by mass of N-phenyl-p-phenylenediamine, stirring and reacting at 75 ℃ at a rotating speed of 180r/min for 30min, removing the toluene at 45 ℃ by a rotary evaporation method after the reaction is finished, adding 15 parts by mass of methanol, stirring at a rotating speed of 180r/min for 1.5min, centrifuging, taking precipitates, washing and drying to obtain antioxidant polysiloxane microspheres;
(5) drying the ethylene-tetrafluoroethylene copolymer at 120 ℃ for 6h according to the mass parts to obtain a dried ethylene-tetrafluoroethylene copolymer; mixing 0.8 part of antioxidant polysiloxane microspheres and 100 parts of dried ethylene-tetrafluoroethylene copolymer, carrying out melting, mixing, extruding, water cooling and grain cutting by using a double-screw extruder to obtain a high-light-transmittance gas film master batch, and then placing the high-light-transmittance gas film master batch into a casting extruder to melt and extrude the high-light-transmittance gas film master batch into a film, wherein the melt temperature is 320 ℃, the diameter of a primary cooling roll is 1000mm, the temperature of the primary cooling roll is 85 ℃, and the high-light-transmittance gas film is obtained and has the thickness of 0.25 mm.
The surfactant is sodium dodecyl benzene sulfonate.
The acid chloride reagent is thionyl chloride.
The temperatures of the first zone to the ninth zone of the double-screw extruder are respectively 295 ℃, 300 ℃, 305 ℃, 310 ℃, 315 ℃, 320 ℃ and 315 ℃, the head temperature is 300 ℃ and the screw rotating speed is 150 r/min.
Example 5
A production method of a high light transmission gas film comprises the following steps:
(1) adding 10 parts by mass of vinyl trimethoxy silane and 1 part by mass of surfactant into 50 parts by mass of hydrochloric acid solution with the pH value of 4.0 at the temperature of 30 ℃, stirring at the rotating speed of 200r/min for 5min, adding sodium hydroxide aqueous solution with the concentration of 0.1mol/L to adjust the pH value to 8, continuously reacting for 6h, neutralizing with hydrochloric acid with the concentration of 0.1mol/L to the pH value of 7, centrifuging to obtain precipitate, washing, drying and crushing to obtain vinyl polysiloxane microspheres;
(2) adding 8 parts by mass of the vinyl polysiloxane microspheres prepared in the step (1) into 50 parts of 12 wt% dilute sulfuric acid, reacting at 70 ℃ for 30min, centrifuging to obtain precipitates, washing and drying to obtain hydroxyl polysiloxane microspheres;
(3) mixing 7 parts by mass of the hydroxyl polysiloxane microspheres prepared in the step (2) with 65 parts by mass of xylene, ultrasonically dispersing for 30min, adding 5 parts by mass of 3-aminopropyltrimethoxysilane, continuously ultrasonically dispersing for 20min, then reacting for 3h at 75 ℃ in a nitrogen atmosphere, cooling to room temperature after the reaction is finished, centrifuging to obtain precipitates, washing and drying to obtain 3-aminopropyltrimethoxysilane grafted polysiloxane microspheres, wherein the ultrasonic frequency is 50kHz, and the power is 160W;
(4) mixing 2 parts by mass of succinic acid, 2 parts by mass of an acylchlorination reagent and 16 parts by mass of toluene, stirring and reacting at 70 ℃ at a rotating speed of 180r/min for 1.5h, adding 3 parts by mass of 3-aminopropyltrimethoxysilane grafted polysiloxane microspheres prepared in the step (3), stirring and reacting at 75 ℃ at a rotating speed of 180r/min for 30min, adding 2 parts by mass of N-phenyl-p-phenylenediamine, stirring and reacting at 75 ℃ at a rotating speed of 180r/min for 30min, removing the toluene at 45 ℃ by a rotary evaporation method after the reaction is finished, adding 15 parts by mass of methanol, stirring at a rotating speed of 180r/min for 1.5min, centrifuging, taking precipitates, washing and drying to obtain antioxidant polysiloxane microspheres;
(5) drying the ethylene-tetrafluoroethylene copolymer at 120 ℃ for 6h according to the mass parts to obtain a dried ethylene-tetrafluoroethylene copolymer; mixing 0.8 part of antioxidant polysiloxane microspheres and 100 parts of dried ethylene-tetrafluoroethylene copolymer, carrying out melting, mixing, extruding, water cooling and grain cutting by using a double-screw extruder to obtain a high-light-transmittance gas film master batch, and then placing the high-light-transmittance gas film master batch into a casting extruder to melt and extrude the high-light-transmittance gas film master batch into a film, wherein the melt temperature is 320 ℃, the diameter of a primary cooling roll is 1000mm, the temperature of the primary cooling roll is 85 ℃, and the high-light-transmittance gas film is obtained and has the thickness of 0.25 mm.
The surfactant is disodium ethylene diamine tetraacetate.
The acid chloride reagent is thionyl chloride.
The temperatures of the first zone to the ninth zone of the double-screw extruder are respectively 295 ℃, 300 ℃, 305 ℃, 310 ℃, 315 ℃, 320 ℃ and 315 ℃, the head temperature is 300 ℃ and the screw rotating speed is 150 r/min.
Comparative example 1
A production method of a high light transmission gas film comprises the following steps:
(1) adding 10 parts by mass of vinyl trimethoxy silane into 50 parts by mass of hydrochloric acid solution with the pH value of 4.0 at the temperature of 30 ℃, stirring at the rotating speed of 200r/min for 5min, adding sodium hydroxide aqueous solution with the concentration of 0.1mol/L to adjust the pH value to 8, continuously reacting for 6h, neutralizing with hydrochloric acid with the concentration of 0.1mol/L to the pH value of 7, centrifuging to obtain precipitate, washing, drying and crushing to obtain vinyl polysiloxane microspheres;
(2) drying the ethylene-tetrafluoroethylene copolymer at 120 ℃ for 6h according to the mass parts to obtain a dried ethylene-tetrafluoroethylene copolymer; mixing 0.8 part of vinyl polysiloxane microspheres, 1 part of N-phenyl-p-phenylenediamine and 100 parts of dried ethylene-tetrafluoroethylene copolymer, carrying out melting, mixing, extruding, water cooling and grain cutting by using a double-screw extruder to obtain a high-light-transmittance gas film master batch, and then placing the high-light-transmittance gas film master batch into a casting extruder to be melted and extruded into a film, wherein the melt temperature is 320 ℃, the diameter of a primary cooling roll is 1000mm, and the temperature of the primary cooling roll is 85 ℃, so that the high-light-transmittance gas film is obtained, and the thickness is 0.25 mm.
The temperatures of the first zone to the ninth zone of the double-screw extruder are respectively 295 ℃, 300 ℃, 305 ℃, 310 ℃, 315 ℃, 320 ℃ and 315 ℃, the head temperature is 300 ℃ and the screw rotating speed is 150 r/min.
Comparative example 2
A production method of a high light transmission gas film comprises the following steps: drying the ethylene-tetrafluoroethylene copolymer at 120 ℃ for 6h according to the mass parts to obtain a dried ethylene-tetrafluoroethylene copolymer; melting, mixing, extruding, water cooling and granulating 100 parts of dried ethylene-tetrafluoroethylene copolymer by a double-screw extruder to obtain high-light-transmission gas film master batch, putting the high-light-transmission gas film master batch into a casting extruder for melting and extruding to form a film, wherein the melt temperature is 320 ℃, the diameter of a primary cooling roller is 1000mm, the temperature of the primary cooling roller is 85 ℃, and the high-light-transmission gas film with the thickness of 0.25mm is obtained.
The temperatures of the first zone to the ninth zone of the double-screw extruder are respectively 295 ℃, 300 ℃, 305 ℃, 310 ℃, 315 ℃, 320 ℃ and 315 ℃, the head temperature is 300 ℃ and the screw rotating speed is 150 r/min.
Test example 1
The haze of the high-light-transmittance gas films obtained in each of the examples and comparative examples was measured by reference to the haze meter method in GB/T2410-. The sample size was: 50mm diameter, 0.25mm thick disc.
The results are shown in Table 1.
Table 1: light transmittance test result
| Transmittance (a) | |
| Example 1 | 79.6 |
| Example 2 | 84.2 |
| Example 3 | 88.1 |
| Example 4 | 86 |
| Example 5 | 86.4 |
| Comparative example 1 | 75.8 |
| Comparative example 2 | 92 |
As can be seen from table 1, the addition of the polysiloxane microspheres leads to a decrease in the light transmittance of the ethylene-tetrafluoroethylene copolymer to some extent, because the polysiloxane microspheres inevitably reflect a part of the light during the process of diffusing the light. From example 3, it can be seen that the transmittance of the high transmittance gas film added with the antioxidant polysiloxane microspheres prepared by the invention is only reduced by 3.9% compared with the transmittance of the pure ethylene-tetrafluoroethylene copolymer in comparative example 2, because the vinyl polysiloxane microspheres with relatively consistent particle size and better dispersibility are obtained by acid-base hydrolysis and the addition of the surfactant to regulate the particle size and independence of the growth of the microspheres; and further carrying out organic synthesis, forming longer antioxidant branched chains on the surface of the polysiloxane microspheres, further enhancing the dispersibility of the prepared polysiloxane microspheres in the ethylene-tetrafluoroethylene copolymer, and avoiding the reduction of light transmittance caused by the agglomeration of the polysiloxane microspheres. Examples 4 and 5 using sodium dodecylbenzenesulfonate or disodium ethylenediaminetetraacetate alone as a surfactant, there was a decrease in light transmittance because the formation and growth of secondary particles during hydrolytic condensation of polysiloxane directly determined the particle size of the final vinylpolysiloxane, so it was critical to prepare monodisperse vinylpolysiloxane that the time for formation of secondary particles was short, ensuring that each secondary particle underwent the same process from formation to growth, contributing to the formation of monodisperse vinylpolysiloxane. Because sodium dodecyl benzene sulfonate is an anionic surfactant, the strong electron-donating ability of the sodium dodecyl benzene sulfonate can activate hydroxyl obtained by methoxy hydrolysis, the condensation polymerization reaction is promoted, the reaction time is shortened, the sodium dodecyl benzene sulfonate and disodium ethylene diamine tetraacetate have synergistic effect, the vinyl polysiloxane microspheres with relatively consistent particle size and good dispersibility are obtained, and the growth time and the nucleation uniformity of the vinyl polysiloxane microspheres can be influenced by only adopting one surfactant, so that the generated polysiloxane microspheres are agglomerated, or the surface is not uniform, and the light diffusion effect and the dispersing performance of the vinyl polysiloxane microspheres are influenced. The light transmittance of the gas film obtained in example 1 was lower than that of example 2 because no surfactant was added during the reaction. The light transmittance of the gas film prepared in example 2 is lower than that of example 3, because a large number of long branched chains exist on the surface of the polysiloxane microspheres after the antioxidant N-phenyl-p-phenylenediamine is grafted, the agglomeration of polysiloxane and ethylene-tetrafluoroethylene copolymer during blending film forming is prevented, and a better dispersion effect is achieved.
Test example 2
The haze of the high-light-transmittance gas films obtained in each of the examples and comparative examples was measured by reference to the haze meter method in GB/T2410-. The sample size was: 50mm diameter, 0.25mm thick disc.
The results are shown in Table 2.
Table 2: haze test results
As can be seen from Table 2, the addition of the polysiloxane microspheres results in a great increase in the haze of the ethylene-tetrafluoroethylene copolymer, and the increase in the haze is inseparable from the dispersibility and particle size of the polysiloxane microspheres. As can be seen from example 3, the haze of the high-transparency air film added with the antioxidant polysiloxane microspheres prepared by the invention is increased by 68.9%, and the haze is greatly improved. The principle is consistent with that of test example 1, the vinyl polysiloxane microspheres with relatively consistent particle size and better dispersibility are obtained mainly due to the regulation and control effect of the surfactant, and the dispersibility of the polysiloxane microspheres is further improved by the grafted antioxidant. In the examples 4 and 5, the sodium dodecyl benzene sulfonate or the disodium ethylene diamine tetraacetate is used as the surfactant independently, the haze of the surfactant is reduced, and the synergistic effect of the sodium dodecyl benzene sulfonate or the disodium ethylene diamine tetraacetate is proved to obtain the polysiloxane microspheres with moderate particle size, uniform surface and good dispersibility. The haze of the film obtained in example 1 is lower than that of the film obtained in example 2 because no surfactant is added during the reaction. The haze of the air film prepared in the example 2 is lower than that of the air film prepared in the example 3, because a large number of long branched chains exist on the surface of the polysiloxane microspheres after the antioxidant N-phenyl-p-phenylenediamine is grafted, the agglomeration of the polysiloxane and the ethylene-tetrafluoroethylene copolymer during blending film forming is prevented, and the better dispersion effect is achieved.
The air film prepared by the invention has high light transmission and high haze, has excellent ageing resistance, and is suitable for manufacturing of air-filled film buildings.
Claims (6)
1. The production method of the high-light-transmittance gas film is characterized by comprising the following steps of:
(1) mixing vinyl trimethoxy silane, a surfactant and hydrochloric acid for reaction, adding an aqueous solution of sodium hydroxide to adjust the pH value to be alkaline, continuously reacting for a period of time, neutralizing with hydrochloric acid until the pH value is 7, centrifuging to obtain a precipitate, washing, drying and crushing to obtain vinyl polysiloxane microspheres;
(2) adding vinyl polysiloxane microspheres into dilute sulfuric acid for heating reaction, centrifuging to obtain precipitate, washing, drying and crushing to obtain hydroxyl polysiloxane microspheres;
(3) adding hydroxyl polysiloxane microspheres and 3-aminopropyltrimethoxysilane into xylene for heating reaction, centrifuging to obtain precipitate, washing and drying to obtain 3-aminopropyltrimethoxysilane grafted polysiloxane microspheres;
(4) mixing succinic acid, an acyl chlorination reagent and toluene, heating for reaction, adding the 3-aminopropyltrimethoxysilane grafted polysiloxane microspheres prepared in the step (3), heating for reaction, adding N-phenyl-p-phenylenediamine, heating for reaction, centrifuging after the reaction is finished, taking precipitate, washing and drying to obtain the antioxidant polysiloxane microspheres;
(5) mixing ethylene-tetrafluoroethylene copolymer and antioxidant polysiloxane microspheres, manufacturing a high light transmission gas film master batch by using a double-screw extruder, and then putting the high light transmission gas film master batch into a casting extruder to melt and extrude the high light transmission gas film master batch into a film to obtain the high light transmission gas film.
2. The method for producing a gas film with high light transmittance according to claim 1, comprising the steps of:
(1) adding 8-12 parts of vinyl trimethoxy silane and 1-2 parts of surfactant into 45-55 parts of hydrochloric acid solution with the pH value of 3.8-4.2 at the temperature of 25-35 ℃, stirring at the rotating speed of 300r/min for 4-6min, adding sodium hydroxide aqueous solution with the concentration of 0.1-0.2mol/L to adjust the pH value of 7.5-9, continuously reacting for 4-8h, neutralizing with hydrochloric acid with the concentration of 0.1-0.2mol/L until the pH value of 7, centrifuging to obtain precipitate, washing, drying and crushing to obtain vinyl polysiloxane microspheres;
(2) adding 6-10 parts by mass of the vinyl polysiloxane microspheres prepared in the step (1) into 45-55 parts by mass of dilute sulfuric acid with the concentration of 10-14 wt%, reacting at 65-75 ℃ for 20-40min, centrifuging, taking out precipitates, washing and drying to obtain hydroxyl polysiloxane microspheres;
(3) mixing 6-8 parts by mass of the hydroxyl polysiloxane microspheres prepared in the step (2) with 50-80 parts by mass of xylene, ultrasonically dispersing for 20-40min, adding 4-6 parts by mass of 3-aminopropyltrimethoxysilane, continuously ultrasonically dispersing for 10-30min, then reacting for 2-4h at 70-80 ℃ in a nitrogen atmosphere, cooling to room temperature after the reaction is finished, centrifuging to obtain precipitates, washing and drying to obtain the 3-aminopropyltrimethoxysilane grafted polysiloxane microspheres, wherein the ultrasonic frequency is 40-60kHz, and the power is 100-200W;
(4) mixing 1-2 parts by mass of succinic acid, 1-2 parts by mass of an acylchlorination reagent and 12-16 parts by mass of toluene, stirring and reacting at 65-75 ℃ and at the rotation speed of 100-200r/min for 1-2h, adding 2-4 parts by mass of 3-aminopropyltrimethoxysilane grafted polysiloxane microspheres prepared in the step (3), stirring and reacting at the rotation speed of 100-200r/min for 30-40min at 70-80 ℃, adding 1-2 parts by mass of N-phenyl-p-phenylenediamine, stirring and reacting at the rotation speed of 100-200r/min for 30-40min at 70-80 ℃, removing the toluene at 40-50 ℃ by a rotary evaporation method after the reaction is finished, adding 10-20 parts by mass of methanol, stirring at the rotation speed of 100-200r/min for 1-2min, centrifuging to obtain precipitate, washing and drying to obtain antioxidant polysiloxane microspheres;
(5) according to the mass parts, the ethylene-tetrafluoroethylene copolymer is dried for 4-8h at the temperature of 110-120 ℃ to obtain a dried ethylene-tetrafluoroethylene copolymer; mixing 0.5-1 part of antioxidant polysiloxane microspheres and 90-110 parts of dried ethylene-tetrafluoroethylene copolymer, carrying out melting, mixing, extruding, water cooling and grain cutting by using a double-screw extruder to obtain high-light-transmittance gas film master batch, and then placing the high-light-transmittance gas film master batch into a casting extruder to be melted and extruded into a film, wherein the melt temperature is 310-.
3. The method for producing a highly translucent gas film according to claim 2 wherein the surfactant is one or a mixture of two or more of sodium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium stearate, and disodium ethylenediaminetetraacetate.
4. The method for producing a gas film having high light transmittance according to claim 2, wherein the acid chloride reagent is one of thionyl chloride, oxalyl chloride and thionyl chloride.
5. The method for producing a high-light-transmittance gas film as claimed in claim 2, wherein the temperatures of the first to ninth zones of the twin-screw extruder are 295-300 ℃, 300-305 ℃, 305-310 ℃, 310-315 ℃, 315-320 ℃, 320-320 ℃, 325-315-320 ℃, the head temperature is 300-305 ℃, and the screw rotation speed is 100-200 r/min.
6. A high light transmittance gas film produced by the method for producing a high light transmittance gas film according to any one of claims 1 to 6.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1294615A (en) * | 1998-12-17 | 2001-05-09 | 蒙岱尔技术有限公司 | Polyolefin graft copolymer/polyamide blend |
| CN102604100A (en) * | 2012-01-19 | 2012-07-25 | 华南理工大学 | Preparation method of monodispersity micron-sized polysilicon microspheres |
| CN103739847A (en) * | 2013-12-17 | 2014-04-23 | 韦兴祥 | Preparation method of organic siloxane microspheres with narrow particle size distribution and richly organized surfaces |
| CN104744700A (en) * | 2015-03-09 | 2015-07-01 | 华南理工大学 | Preparation method of mono-dispersion polysiloxane microspheres with controllable particle size |
| WO2016089817A1 (en) * | 2014-12-05 | 2016-06-09 | Momentive Performance Materials Japan Llc | Organosiloxane composition having high refractive index and applications containing the same |
| US20160297965A1 (en) * | 2015-04-10 | 2016-10-13 | China Petroleum & Chemical Corporation | Resin Composition Having Improved Haze and Light Transmittance and Process for Preparing the Same |
| CN106432733A (en) * | 2016-09-28 | 2017-02-22 | 北京石油化工学院 | Method for preparing narrow-size-dispersion ultrafine polyvinyl siloxane crosslinked microspheres |
| CN106589384A (en) * | 2016-12-27 | 2017-04-26 | 浙江新安化工集团股份有限公司 | Preparation method of modified polysiloxane microspheres with controllable particle sizes |
-
2022
- 2022-01-07 CN CN202210017917.7A patent/CN114316422A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1294615A (en) * | 1998-12-17 | 2001-05-09 | 蒙岱尔技术有限公司 | Polyolefin graft copolymer/polyamide blend |
| CN102604100A (en) * | 2012-01-19 | 2012-07-25 | 华南理工大学 | Preparation method of monodispersity micron-sized polysilicon microspheres |
| CN103739847A (en) * | 2013-12-17 | 2014-04-23 | 韦兴祥 | Preparation method of organic siloxane microspheres with narrow particle size distribution and richly organized surfaces |
| WO2016089817A1 (en) * | 2014-12-05 | 2016-06-09 | Momentive Performance Materials Japan Llc | Organosiloxane composition having high refractive index and applications containing the same |
| CN104744700A (en) * | 2015-03-09 | 2015-07-01 | 华南理工大学 | Preparation method of mono-dispersion polysiloxane microspheres with controllable particle size |
| US20160297965A1 (en) * | 2015-04-10 | 2016-10-13 | China Petroleum & Chemical Corporation | Resin Composition Having Improved Haze and Light Transmittance and Process for Preparing the Same |
| CN106432733A (en) * | 2016-09-28 | 2017-02-22 | 北京石油化工学院 | Method for preparing narrow-size-dispersion ultrafine polyvinyl siloxane crosslinked microspheres |
| CN106589384A (en) * | 2016-12-27 | 2017-04-26 | 浙江新安化工集团股份有限公司 | Preparation method of modified polysiloxane microspheres with controllable particle sizes |
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