WO2022062245A1 - High transparent tpu film for electronic products and preparation method therefor - Google Patents

High transparent tpu film for electronic products and preparation method therefor Download PDF

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WO2022062245A1
WO2022062245A1 PCT/CN2020/140449 CN2020140449W WO2022062245A1 WO 2022062245 A1 WO2022062245 A1 WO 2022062245A1 CN 2020140449 W CN2020140449 W CN 2020140449W WO 2022062245 A1 WO2022062245 A1 WO 2022062245A1
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parts
electronic products
tpu film
preparation
mixing
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PCT/CN2020/140449
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French (fr)
Chinese (zh)
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何建雄
杨博
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何建雄
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18Manufacture of films or sheets
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/2805Compounds having only one group containing active hydrogen
    • C08G18/288Compounds containing at least one heteroatom other than oxygen or nitrogen
    • C08G18/2885Compounds containing at least one heteroatom other than oxygen or nitrogen containing halogen atoms
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30Low-molecular-weight compounds
    • C08G18/32Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203Polyhydroxy compounds
    • C08G18/3206Polyhydroxy compounds aliphatic
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/42Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4236Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
    • C08G18/4238Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/48Polyethers
    • C08G18/4833Polyethers containing oxyethylene units
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6603Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6607Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/02Elements
    • C08K3/04Carbon
    • C08K3/042Graphene or derivatives, e.g. graphene oxides
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00Use of pretreated ingredients
    • C08K9/08Ingredients agglomerated by treatment with a binding agent
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04Polyurethanes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00Use of ingredients characterised by shape
    • C08K7/22Expanded, porous or hollow particles
    • C08K7/24Expanded, porous or hollow particles inorganic
    • C08K7/26Silicon- containing compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00Use of pretreated ingredients
    • C08K9/04Ingredients treated with organic substances
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00Use of pretreated ingredients
    • C08K9/04Ingredients treated with organic substances
    • C08K9/06Ingredients treated with organic substances with silicon-containing compounds

Definitions

  • the invention belongs to the technical field of polymer materials, in particular to a TPU film and a preparation method thereof, in particular to a high-transparency TPU film for electronic products and a preparation method thereof.
  • Thermoplastic polyurethane is a new type of organic polymer synthetic material with excellent properties, which can replace rubber and soft polyvinyl chloride material PVC.
  • PVC polyvinyl chloride
  • it has excellent physical properties, such as abrasion resistance and resilience, which are better than ordinary polyurethane and PVC, and its aging resistance is better than rubber. It can be said that it is the most ideal material to replace PVC and PU.
  • commercially available TPU materials generally have shortcomings such as poor heat resistance and insufficient transparency. Long-term exposure to high temperature environments is prone to deterioration, and at the same time, yellowing occurs, which affects the normal use and function of the film.
  • CN104262937A discloses a high-transparency TPU film for keyboard film, which by mass percentage contains 5-20% of PP particles; 40-80% of TPU particles; 5-20% of epoxy resin; phosphite without benzene ring 1 -5%; maleic anhydride graft copolymer polypropylene 1-5%; UV absorber 1-5%; hydrogen-containing silicone oil 1-5%.
  • the invention improves the transparency and mechanical properties of the TPU film, but its transparency drops sharply under long-term exposure, and the mechanical properties also weaken.
  • CN110481131A provides and discloses a high-transparency polyether type double-mirror TPU film, including a TPU film body, and the top and bottom of the TPU film body are provided with tear-proof layers.
  • the present invention is provided with a tear-proof layer, a transparent vulcanized rubber layer, a transparent thermoplastic rubber layer, a transparent polyolefin layer, a flame retardant layer, a transparent flame retardant silicone rubber layer, a transparent flame retardant magnesium oxide layer, a transparent flame retardant polyamide layer, and a flame retardant layer.
  • the corrosion layer, the transparent phenolic plastic layer, the transparent epoxy resin layer and the transparent polyisobutylene rubber layer cooperate with each other to improve the tear resistance of the TPU film.
  • the TPU film is made of highly transparent material for each layer, its transparency is related to the purity and uniformity of the medium. Too many layers will cause the transparency to drop sharply after long-term exposure, which cannot meet the application requirements in the technical field of some electronic products.
  • the purpose of the present invention is to provide a transparent TPU film and a preparation method thereof, in particular to provide a highly transparent TPU film for electronic products and a preparation method thereof.
  • the TPU film material described in this application has extremely high transparency and excellent mechanical properties.
  • "high transparency" in the present invention means that the light transmittance is above 97%.
  • the present invention provides a high-transparency TPU film for electronic products, and the preparation raw materials of the high-transparency TPU film for electronic products include the following components in parts by weight:
  • polyester polyol and isophorone diisocyanate are used as main raw materials to synthesize polyurethane, and an appropriate proportion of polyethylene glycol is introduced into the polyurethane segment, and the hard and soft segments in the polyurethane segment can form a more suitable
  • the microphase separation structure increases the content force of the rigid segment, thereby improving the tensile strength and elongation of the film.
  • the introduction of fluorine-containing polyols is end-capped with fluorine to obtain double cross-linked polyurethane, which endows the film with excellent optical transparency and flexibility due to the good compatibility of the fluorine-containing polyol with the polyurethane segment and the small roughness of the film. and the introduction of fluorine as a hydrophobic segment, endows the film with better self-cleaning and anti-adhesion properties.
  • the present invention introduces modified graphene oxide to modify the polyurethane, which can react with polyols and isocyanates, and can act as the hard segment of TPU, so that a part of chemical cross-linking structure is formed between molecules, and the mechanical properties of the material are improved.
  • modified porous silica can form hydrogen bonds or generate van der Waals forces due to the presence of a large number of hydroxyl groups on the surface of porous silica materials. It is the hydroxyl group on silanol that plays an adsorption role in the TPU system, which constitutes the adsorption center.
  • adsorbents have a huge surface area and pore volume, so they have a good ability to adsorb polar impurities, and the metal ions in the modified polyurethane system can be on the surface of the adsorbent, thereby further improving the light transmittance of the TPU film.
  • the weight part of polyester polyol is 45-55 parts, for example, it can be 45 parts, 46 parts, 47 parts, 48 parts, 49 parts, 50 parts, 51 parts, 52 parts, 53 parts, 54 parts servings, 55 servings, etc.
  • the weight part of polyethylene glycol is 3-10 parts, for example, it can be 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, etc.
  • the weight part of the fluorine-containing polyol is 1-5 parts, for example, 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, etc.
  • the weight part of isophorone diisocyanate is 25-35 parts, for example, it can be 25 parts, 26 parts, 27 parts, 28 parts, 29 parts, 30 parts, 31 parts, 32 parts, 33 parts , 34 copies, 35 copies, etc.
  • the weight part of the chain extender is 5-10 parts, for example, it can be 5 parts, 5.5 parts, 6 parts, 6.5 parts, 7 parts, 7.5 parts, 8 parts, 8.5 parts, 9 parts, 9.5 parts , 10 copies, etc.
  • the parts by weight of modified graphene oxide are 1-5 parts, such as 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, etc. .
  • the weight part of the catalyst is 0.1-0.5 part, for example, it can be 0.1 part, 0.2 part, 0.3 part, 0.4 part, 0.5 part, etc.
  • the polyester polyol comprises polybutylene succinate, polybutylene adipate, polyhexamethylene adipate or polybutylene ethylene adipate. Any one or a combination of at least two.
  • the number average molecular weight of the polyester polyol is 1000-3000, for example, it can be 1000, 1200, 1400, 1600, 1800, 2000, 2200, 2400, 2600, 2800, 3000 and the like.
  • the number average molecular weight of the polyethylene glycol is 400-2000, for example, it can be 400, 600, 8000, 1000, 1200, 1400, 1600, 1800, 2000 and the like.
  • the fluorine-containing polyol comprises any one or at least two of perfluoropolyether alcohol, tridecafluoro-n-octanol, hexafluoro-n-propanol, hexafluoroisopropanol or hexafluoro-n-butanol combination, preferably tridecafluoro-n-octanol and/or hexafluoro-n-butanol.
  • the chain extender includes any one or a combination of at least two of ethylene glycol, 1,3-propanediol, 1,4-butanediol or 1,3-hexanediol.
  • the modified graphene oxide is chitosan modified graphene oxide.
  • the preparation method of the chitosan-modified graphene oxide is as follows: after the graphene oxide is dispersed in a solvent (such as THF, DMF, etc.), after adding chitosan, after ultrasonic dispersion, react at room temperature for more than 10 hours
  • the chitosan-modified graphene oxide can be obtained.
  • Chitosan-graphene oxide is obtained by modifying graphene oxide with chitosan. Chitosan contains a large number of amino groups and hydroxyl groups, which can produce strong hydrogen bonds with graphene oxide.
  • the raw materials for the preparation of the modified porous silica include in parts by weight: 100 parts of silica, 1-5 parts of ammonia water, 1-5 parts of surfactant, 0.5-2 parts of silane coupling agent and 50-60 parts of solvent.
  • the weight fraction of ammonia water is 1-5 parts, for example, it can be 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts servings, 5 servings, etc.
  • the weight part of the surfactant is 1-5 parts, for example, it can be 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts , 4.5 copies, 5 copies, etc.
  • the weight part of the silane coupling agent is 0.5-2 parts, for example, it can be 0.5 part, 0.6 part, 0.7 part, 0.8 part, 0.9 part, 1 part, 1.2 part servings, 1.4 servings, 1.6 servings, 1.8 servings, 2 servings, etc.
  • the weight of the solvent is 50-60 parts, such as 50 parts, 51 parts, 52 parts, 53 parts, 54 parts, 55 parts, 56 parts, 57 parts 58, 59, 60, etc.
  • the surfactant is a cationic surfactant, preferably one of dodecyltrimethylammonium bromide, cetyltrimethylammonium bromide or octadecyltrimethylammonium bromide any one or a combination of at least two.
  • the silane coupling agent is an epoxy group-containing silane coupling agent, preferably ⁇ -glycidoxypropyltrimethoxysilane.
  • the solvent is THF and/or DMF.
  • the modified porous silica is prepared by the following preparation method: mixing silica, ammonia water and a solvent, performing a preheating reaction, then adding a cationic surfactant and a silane coupling agent, mixing and stirring, to obtain The modified porous silica.
  • the temperature of the preheating reaction is 120-130°C, such as 120°C, 122°C, 124°C, 126°C, 128°C, 130°C, etc.
  • the time of the preheating reaction is 1-2h, For example, it can be 1h, 1.2h, 1.4h, 1.6h, 1.8h, 2h and so on.
  • the temperature of the mixing and stirring is 140-160°C, such as 140°C, 142°C, 146°C, 148°C, 150°C, 152°C, 154°C, 156°C, 158°C, 160°C, etc.
  • the mixing and stirring time is 40-50min, such as 40min, 42min, 44min, 46min, 48min, 50min, etc.
  • the specific surface area of the modified porous silica is 600-800 m 2 /g, such as 600 m 2 /g, 620 m 2 /g, 640 m 2 /g, 660 m 2 /g, 680 m 2 /g, 700m 2 /g, 720m 2 /g, 740m 2 /g, 760m 2 /g, 780m 2 /g, 800m 2 /g, etc.
  • the average pore diameter of the pores of the modified porous silica is 30-50nm, For example, it can be 30 nm, 32 nm, 34 nm, 36 nm, 38 nm, 40 nm, 42 nm, 44 nm, 46 nm, 48 nm, 50 nm and the like.
  • the catalyst comprises any one or a combination of at least two of dibutyltin dilaurate, stannous octoate or cobalt octoate.
  • the present invention provides a preparation method of the high-transparency TPU film for electronic products as described in the first aspect, the preparation method comprising the following steps:
  • step (2) mixing the polyurethane prepolymer obtained in step (1), modified graphene oxide and chain extender, and reacting to obtain a polyurethane elastomer;
  • step (3) mixing and stirring the polyurethane elastomer obtained in step (2) and the modified porous silica, and extrusion molding to obtain the high-transparency TPU film for electronic products.
  • the temperature of the reaction in step (1) is 80-120°C, such as 80°C, 90°C, 100°C, 110°C, 120°C, etc.
  • the reaction time is 2-4h, for example, it can be 2h, 2.5h, 3h, 3.5h, 4h, etc.
  • the temperature of the reaction in step (2) is 70-80°C, such as 70°C, 72°C, 74°C, 76°C, 78°C, 80°C, etc.
  • the reaction time is 2-4h, For example, it can be 2h, 2.5h, 3h, 3.5h, 4h and so on.
  • the temperature of the mixing and stirring in step (3) is 50-60°C, for example, it can be 50°C, 52°C, 54°C, 56°C, 58°C, 60°C, etc.
  • the mixing and stirring time is 20- 30min, for example, can be 20min, 22min, 24min, 26min, 28min, 30min and the like.
  • the extrusion molding in step (3) is performed with a twin-screw extruder
  • the temperature of the mixing section of the twin-screw extruder is 160-170°C, for example, 160°C, 162°C, 164°C, 166°C °C, 168 °C, 170 °C, etc.
  • the temperature of the extrusion section of the twin-screw extruder is 170-180 °C, for example, it can be 170 °C, 172 °C, 174 °C, 176 °C, 178 °C, 180 °C, etc.
  • the temperature of the die head of the twin-screw extruder is 160-170°C, such as 160°C, 162°C, 164°C, 166°C, 168°C, 170°C, and the like.
  • the preparation method of the highly transparent TPU film for electronic products comprises the following steps:
  • step (2) mixing the polyurethane prepolymer obtained in step (1), the modified graphene oxide and the chain extender, and reacting at 70-80° C. for 2-4 hours to obtain a polyurethane elastomer;
  • step (3) The polyurethane elastomer obtained in step (2) and the modified porous silica are mixed and stirred at 50-60° C. for 20-30 minutes, and extruded by a twin-screw extruder.
  • the mixing section of the twin-screw extruder The temperature is 160-170°C, the temperature of the extrusion section of the twin-screw extruder is 170-180°C, and the temperature of the head of the twin-screw extruder is 160-170°C, and then the single-screw extruder is used for extrusion casting. Film-forming or blow-molding film-forming to obtain the high-transparency TPU film for electronic products.
  • the present invention has the following beneficial effects:
  • the TPU film material of the present invention is composed of polyester polyol, polyethylene glycol, fluorine-containing polyol, isophorone diisocyanate, chain extender, modified graphene oxide, modified porous diisocyanate in appropriate proportions.
  • the silicon oxide and the catalyst are prepared, and on the basis of ensuring the excellent transparency of the TPU film material, it also has small roughness and excellent mechanical properties, and is more suitable for the protection of electronic products.
  • the light transmittance of the TPU film material of the present invention is above 97%, the roughness is below 5nm, the tensile strength is above 60-70MPa, and the elongation at break is 800-1000%.
  • This preparation example provides a modified porous silica I, which is prepared by the following preparation method: 100 g of silica, 3 g of 25 wt % ammonia water and 50 g of THF are mixed, and the mixture is mixed at 120 After preheating the reaction for 2 hours, 2g of cetyltrimethylammonium bromide and 1g of ⁇ -glycidyloxypropyltrimethoxysilane were added, and the mixture was mixed and stirred at 150°C for 45min to obtain a specific surface area of 750m 2 /g, modified porous silica I with an average pore size of 45 nm.
  • This preparation example provides a modified porous silica II.
  • the modified porous silica II is prepared by the following preparation method: 100 g of silica, 2 g of 25 wt % ammonia water and 60 g of THF are mixed at 130 After preheating the reaction for 1 h, 3 g of dodecyl trimethyl ammonium bromide and 1 g of ⁇ -glycidyloxypropyltrimethoxysilane were added, and the mixture was mixed and stirred at 150 ° C for 45 min to obtain a specific surface area of 730 m 2 /g, modified porous silica II with an average pore size of 42 nm.
  • This preparation example provides a modified porous silica III.
  • the modified porous silica III is prepared by the following preparation method: 100 g of silica, 4 g of 25 wt% ammonia water and 60 g of THF are mixed at 120 After preheating the reaction for 1 h, 2 g of octadecyltrimethylammonium bromide and 1 g of ⁇ -glycidyloxypropyltrimethoxysilane were added, and the mixture was mixed and stirred at 150 °C for 45 minutes to obtain a specific surface area of 690 m 2 /g, modified porous silica III with an average pore size of 38 nm.
  • This preparation example provides a modified porous silica IV
  • the modified porous silica IV is prepared by the following preparation method: 100 g of silica, 3 g of 25 wt % ammonia water and 50 g of THF are mixed, and the mixture is mixed at 120 After preheating the reaction at °C for 2h, add 2g of sodium dodecylbenzenesulfonate and 1g of ⁇ -glycidyloxypropyltrimethoxysilane, mix and stir at 150°C for 45min, to obtain a specific surface area of 620m 2 / g, Modified porous silica IV with an average pore size of 33 nm.
  • This preparation example provides a modified porous silica V
  • the modified porous silica V is prepared by the following preparation method: 100 g of silica, 3 g of 25wt% ammonia water and 50 g of THF are mixed, After preheating the reaction for 2 hours at °C, 1 g of ⁇ -glycidyloxypropyltrimethoxysilane was added, and the mixture was mixed and stirred at 150 °C for 45 minutes to obtain a modified porous bilayer with a specific surface area of 580 m 2 /g and an average pore diameter of 28 nm. Silicon oxide V.
  • This preparation example provides a chitosan-modified graphene oxide
  • the chitosan-modified graphene oxide is prepared by the following preparation method: disperse 100 g of graphene oxide in 50 mL of THF, add 10 g of chitosan , ultrasonic dispersion was carried out, the ultrasonic power was 600W, and the grafting reaction was carried out by stirring at 200 r/min at 25 °C for 12 h to obtain a chitosan modified graphene oxide dispersion, which was concentrated and dried to obtain a chitosan modified oxidation solution.
  • Graphene disperse 100 g of graphene oxide in 50 mL of THF, add 10 g of chitosan , ultrasonic dispersion was carried out, the ultrasonic power was 600W, and the grafting reaction was carried out by stirring at 200 r/min at 25 °C for 12 h to obtain a chitosan modified graphene oxide dis
  • the present embodiment provides a high-transparency TPU film for electronic products, and the preparation raw materials of the high-transparency TPU film for electronic products include the following components in parts by weight:
  • the number-average molecular weight of polybutylene adipate is 2000
  • the number-average molecular weight of polyethylene glycol is 800
  • the modified porous silica is modified porous silica I provided in Preparation Example 1.
  • step (2) mixing the polyurethane prepolymer obtained in step (1), chitosan-modified graphene oxide and ethylene glycol, and reacting at 75° C. for 3 hours to obtain a polyurethane elastomer;
  • step (3) The polyurethane elastomer obtained in step (2) and the modified porous silica I were mixed and stirred at 50° C. for 30 min, and extruded by a twin-screw extruder, and the temperature of the mixing section of the twin-screw extruder was 160°C °C, the temperature of the extrusion section of the twin-screw extruder is 180 °C, and the temperature of the head of the twin-screw extruder is 160 °C, and then the single-screw extrusion is used to cast a film to obtain the electronic product. High transparent TPU film.
  • the present embodiment provides a high-transparency TPU film for electronic products, and the preparation raw materials of the high-transparency TPU film for electronic products include the following components in parts by weight:
  • the number average molecular weight of polybutylene adipate is 1000
  • the number average molecular weight of polyethylene glycol is 1000
  • the modified porous silica is modified porous silica II provided in Preparation Example 2.
  • step (2) mixing the polyurethane prepolymer obtained in step (1), chitosan-modified graphene oxide and ethylene glycol, and reacting at 75° C. for 3 hours to obtain a polyurethane elastomer;
  • step (3) The polyurethane elastomer obtained in step (2) and the modified porous silica II were mixed and stirred at 50° C. for 30 minutes, and extruded by a twin-screw extruder, and the temperature of the mixing section of the twin-screw extruder was 170° C. °C, the temperature of the extrusion section of the twin-screw extruder is 180 °C, and the temperature of the head of the twin-screw extruder is 160 °C, and then the single-screw extrusion is used to cast a film to obtain the electronic product. High transparent TPU film.
  • the present embodiment provides a high-transparency TPU film for electronic products, and the preparation raw materials of the high-transparency TPU film for electronic products include the following components in parts by weight:
  • the number average molecular weight of polybutylene adipate is 2000
  • the number average molecular weight of polyethylene glycol is 600
  • the modified porous silica is modified porous silica III provided in Preparation Example 3.
  • step (2) mixing the polyurethane prepolymer obtained in step (1), chitosan-modified graphene oxide and ethylene glycol, and reacting at 75° C. for 3 hours to obtain a polyurethane elastomer;
  • step (3) The polyurethane elastomer obtained in step (2) and the modified porous silica III were mixed and stirred at 50° C. for 30 minutes, and extruded by a twin-screw extruder.
  • the temperature of the mixing section of the twin-screw extruder was 170 °C
  • the temperature of the extrusion section of the twin-screw extruder is 180 °C
  • the temperature of the head of the twin-screw extruder is 160 °C
  • the single-screw extrusion is used to cast a film to obtain the electronic product.
  • High transparent TPU film High transparent TPU film.
  • This embodiment provides a high-transparency TPU film for electronic products.
  • the only difference from Embodiment 1 is that the modified porous silica I is replaced with an equivalent mass of six-modified porous silica IV, and the contents of other components and The preparation method is the same as in Example 1.
  • This embodiment provides a high-transparency TPU film for electronic products.
  • the only difference from Embodiment 1 is that the modified porous silica I is replaced with the same quality of modified porous silica V, and the contents of other components and the preparation
  • the method is the same as in Example 1.
  • This embodiment provides a high-transparency TPU film for electronic products.
  • the only difference from Embodiment 1 is that tridecafluoro-n-octanol is replaced with hexafluoroisopropanol of the same quality, and the contents and preparation methods of other components are the same as in the implementation. example 1.
  • This embodiment provides a high-transparency TPU film for electronic products.
  • the only difference from Embodiment 1 is that the content of polyethylene glycol is 1 part, the content of tridecafluoro-n-octanol is 11 parts, and the content of other components and
  • the preparation method is the same as in Example 1.
  • This embodiment provides a high-transparency TPU film for electronic products.
  • the only difference from Embodiment 1 is that the content of polyethylene glycol is 11 parts, the content of tridecafluoro-n-octanol is 1 part, and the content of other components and
  • the preparation method is the same as in Example 1.
  • This comparative example provides a high-transparency TPU film for electronic products.
  • the only difference from Example 1 is that polyethylene glycol is not added, the content of polybutylene adipate is increased to 58 parts, and the content and preparation of other components The method is the same as in Example 1.
  • This comparative example provides a high-transparency TPU film for electronic products.
  • the difference from Example 1 is that no tridecafluoro-n-octanol is added, the content of polybutylene adipate is increased to 54 parts, and the content of other components is And the preparation method is the same as Example 1.
  • This comparative example provides a high-transparency TPU film for electronic products.
  • the difference from Example 1 is that isophorone diisocyanate is replaced with hexamethylene diisocyanate of the same quality, and the contents and preparation methods of other components are the same Example 1.
  • This comparative example provides a highly transparent TPU film for electronic products.
  • the only difference from Example 1 is that chitosan-modified graphene oxide is not added, the content of modified porous silica is increased to 5 parts, and other components
  • the content and preparation method are the same as those in Example 1.
  • This comparative example provides a highly transparent TPU film for electronic products.
  • the only difference from Example 1 is that no modified porous silica is added, the content of chitosan-modified graphene oxide is increased to 5 parts, and other components are The content and preparation method are the same as those in Example 1.
  • This comparative example provides a high-transparency TPU film for electronic products, and the difference from Example 1 is only that the modified graphene oxide is replaced with graphene oxide of equal quality, and the content of other components and the preparation method are the same as those of Example 1.
  • This comparative example provides a high-transparency TPU film for electronic products.
  • the only difference from Example 1 is that the modified porous silica is replaced with silica of equal quality, and the contents and preparation methods of other components are the same as those of Example 1. .
  • Example 1 99.5 3.9 68 960 Example 2 99.2 3.9 70 980
  • Example 3 99.5 4.0 69 950
  • Example 4 99.0 4.5 66 920
  • Example 5 97.5 4.5 67 890
  • Example 6 98.2 4.2 65
  • Example 7 98.0 4.6 62 860
  • Example 8 97.8 4.5 63
  • Comparative Example 1 91.5 6.8 52
  • Comparative Example 2 92.3 7.2 51 730
  • Comparative Example 3 90.5 6.5 48
  • Comparative Example 4 95.2 12.0 46 650
  • Comparative Example 5 89.9 8.2 42 Comparative Example 6 91.6 15.4 52 700
  • the light transmittance of the TPU film material of the present invention is above 97%, the roughness is below 5nm, the tensile strength is above 60-70MPa, and the elongation at break is 800-1000%.
  • the TPU film material of the present invention is composed of appropriate proportions of polyester polyol, polyethylene glycol, fluorine-containing polyol, isophorone diisocyanate, chain extender, modified graphene oxide, modified porous silica
  • the catalyst is prepared, on the basis of ensuring the excellent transparency of the TPU film material, it also has small roughness and excellent mechanical properties, and is more suitable for the protection of electronic products.
  • Example 1 and Examples 4 and 5 From the comparison between Example 1 and Examples 4 and 5, it can be seen that the cationic surfactant helps to form modified porous silica with high surface area and high pore size, so as to more reliably adsorb metal ions to further improve the light transmittance of the film , and reduce its roughness. From the comparison of Example 1 and Examples 7 and 8, it can be seen that when the ratio of polyethylene glycol and tridecafluoro-n-octanol is within the scope of the application, the prepared TPU film material has more excellent transparency and flexibility and is more flexible. small roughness.
  • Example 1 and Comparative Example 1 lack of polyethylene glycol, the content of the rigid segment cannot be well increased, so the tensile strength and elongation of the film decrease significantly. From Example 1 and Comparative Example 2, lack of fluorine-containing polyol, the optical transparency and flexibility of the film decreased significantly. It can be seen from the comparison between Example 1 and Comparative Example 3 that the film formed by isophorone diisocyanate is more transparent, because the isophorone diisocyanate molecule is asymmetric and difficult to form crystals.
  • Example 1 From the comparison of Example 1 and Comparative Examples 4-7, it can be seen that when the modified graphene oxide and modified porous silica are not added, or the two are replaced with unmodified graphene oxide and The optical transparency and flexibility decreased significantly, and the roughness increased significantly.
  • the present invention describes the high-transparency TPU film for electronic products and its preparation method by the above-mentioned embodiments, but the present invention is not limited to the above-mentioned embodiments, that is to say, it does not mean that the present invention can only be implemented by relying on the above-mentioned embodiments. .
  • Those skilled in the art should understand that any improvement of the present invention, the equivalent replacement of each raw material of the product of the present invention, the addition of auxiliary components, the selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

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Abstract

The present invention provides a high transparent TPU film for electronic products and a preparation method therefor. The raw materials for preparing the high transparent TPU film for electronic products comprise the following components in parts by weight: 45-55 parts of polyester polyol, 3-10 parts of polyethylene glycol, 1-5 parts of fluorine-containing polyol, 25-35 parts of isophorone diisocyanate, 5-10 parts of chain extender, 1-5 parts of modified graphene oxide, 1-5 parts of modified porous silicon dioxide, and 0.1-0.5 part of catalyst. The TPU film material of the present invention also has relatively low roughness and good mechanical properties while having excellent transparency, and is more suitable for the protection of electronic products.

Description

一种电子产品用高透明TPU薄膜及其制备方法A kind of high transparent TPU film for electronic products and preparation method thereof
本公开基于申请号为202011002031.2,申请日为2020年09月22日的中国专利申请提出,并要求该中国专利申请的优先权,该中国专利申请的全部内容在此引入本申请作为参考。The present disclosure is based on the Chinese patent application with the application number of 202011002031.2 and the filing date of September 22, 2020, and claims the priority of the Chinese patent application. The entire content of the Chinese patent application is incorporated herein by reference.
技术领域technical field
本发明属于高分子材料技术领域,具体涉及一种TPU薄膜及其制备方法,尤其涉及一种电子产品用高透明TPU薄膜及其制备方法。The invention belongs to the technical field of polymer materials, in particular to a TPU film and a preparation method thereof, in particular to a high-transparency TPU film for electronic products and a preparation method thereof.
背景技术Background technique
热塑性聚氨酯(TPU)是一种新型的有机高分子合成材料,其各项性能优异,可以代替橡胶、软性聚氯乙烯材料PVC。例如其具有优异的物理性能,例如耐磨性,回弹力都好过普通聚氨酯和PVC,耐老化性好过橡胶,可以说是替代PVC和PU的最理想的材料。目前,市售的TPU材料普遍存在耐热性差和透明性不足等缺点,长期暴露于高温环境中很容易发生变质,同时产生黄变现象,影响薄膜的正常使用和功能发挥。Thermoplastic polyurethane (TPU) is a new type of organic polymer synthetic material with excellent properties, which can replace rubber and soft polyvinyl chloride material PVC. For example, it has excellent physical properties, such as abrasion resistance and resilience, which are better than ordinary polyurethane and PVC, and its aging resistance is better than rubber. It can be said that it is the most ideal material to replace PVC and PU. At present, commercially available TPU materials generally have shortcomings such as poor heat resistance and insufficient transparency. Long-term exposure to high temperature environments is prone to deterioration, and at the same time, yellowing occurs, which affects the normal use and function of the film.
CN104262937A公开了一种用于键盘膜的高透明TPU薄膜,其按质量百分比含有PP粒子5-20%;TPU颗粒40-80%;环氧树脂5-20%;无苯环的亚磷酸酯1-5%;马来酸酐接枝共聚聚丙烯1-5%;紫外线吸收剂1-5%;含氢硅油1-5%。该发明改进了TPU薄膜的透明度和机械性能,但长期暴露下其透明度急剧下降,机械性能也有所减弱。CN104262937A discloses a high-transparency TPU film for keyboard film, which by mass percentage contains 5-20% of PP particles; 40-80% of TPU particles; 5-20% of epoxy resin; phosphite without benzene ring 1 -5%; maleic anhydride graft copolymer polypropylene 1-5%; UV absorber 1-5%; hydrogen-containing silicone oil 1-5%. The invention improves the transparency and mechanical properties of the TPU film, but its transparency drops sharply under long-term exposure, and the mechanical properties also weaken.
CN110481131A提供了公开了一种高透明聚醚型双镜面TPU薄膜,包括TPU薄膜本体,所述TPU薄膜本体的顶部和底部均设置有防撕裂层。本发明通过设置防撕裂层、透明硫化橡胶层、透明热塑橡胶层、透明聚烯烃层、阻燃层、透明阻燃硅橡胶层、透明阻燃氧化镁层、透明阻燃聚酰胺层、耐腐蚀层、透明 酚醛塑料层、透明环氧树脂层和透明聚异丁烯橡胶层相互配合,达到了提高TPU薄膜的防撕裂性能。虽然,该TPU薄膜虽然每层选择高透明材料,其透明度与介质的纯净和均匀程度有关,层数过多导致其长期暴露后,透明度急剧下降,无法满足一些电子产品技术领域的应用要求。CN110481131A provides and discloses a high-transparency polyether type double-mirror TPU film, including a TPU film body, and the top and bottom of the TPU film body are provided with tear-proof layers. The present invention is provided with a tear-proof layer, a transparent vulcanized rubber layer, a transparent thermoplastic rubber layer, a transparent polyolefin layer, a flame retardant layer, a transparent flame retardant silicone rubber layer, a transparent flame retardant magnesium oxide layer, a transparent flame retardant polyamide layer, and a flame retardant layer. The corrosion layer, the transparent phenolic plastic layer, the transparent epoxy resin layer and the transparent polyisobutylene rubber layer cooperate with each other to improve the tear resistance of the TPU film. Although the TPU film is made of highly transparent material for each layer, its transparency is related to the purity and uniformity of the medium. Too many layers will cause the transparency to drop sharply after long-term exposure, which cannot meet the application requirements in the technical field of some electronic products.
因此,开发一种高透明的并且具有优异的力学性能的TPU薄膜是电子产品领域研究的重点。Therefore, the development of a highly transparent TPU film with excellent mechanical properties is the focus of research in the field of electronic products.
发明内容SUMMARY OF THE INVENTION
针对现有技术的不足,本发明的目的在于提供一种透明TPU薄膜及其制备方法,特别是提供一种电子产品用高透明TPU薄膜及其制备方法。本申请所述TPU薄膜材料具有极高的透明度和优异的力学性能。特别地,本发明所述“高透明”指的是透光率在97%以上。In view of the deficiencies of the prior art, the purpose of the present invention is to provide a transparent TPU film and a preparation method thereof, in particular to provide a highly transparent TPU film for electronic products and a preparation method thereof. The TPU film material described in this application has extremely high transparency and excellent mechanical properties. In particular, "high transparency" in the present invention means that the light transmittance is above 97%.
为达此目的,本发明采用以下技术方案:For this purpose, the present invention adopts the following technical solutions:
第一方面,本发明提供一种电子产品用高透明TPU薄膜,所述电子产品用高透明TPU薄膜的制备原料按重量份数计包括如下组分:In the first aspect, the present invention provides a high-transparency TPU film for electronic products, and the preparation raw materials of the high-transparency TPU film for electronic products include the following components in parts by weight:
Figure PCTCN2020140449-appb-000001
Figure PCTCN2020140449-appb-000001
在本发明中,以聚酯多元醇和异佛尔酮二异氰酸酯为主体原料合成聚氨酯, 并在聚氨酯链段中引入适当比例的聚乙二醇,聚氨酯链段中的硬软段可形成较合适的微相分离结构,增加刚性链段的含量作用力,从而提高薄膜的拉伸强度和伸长率。此外,含氟多元醇的引入以氟封端得到双交联聚氨酯,由于含氟多元醇与聚氨酯链段的相容性良好以及薄膜的粗糙度较小,从而赋予薄膜具有优异的光学透明度和柔韧性,且引入氟作为疏水链段,赋予薄膜较好的自清洁性和抗粘性。In the present invention, polyester polyol and isophorone diisocyanate are used as main raw materials to synthesize polyurethane, and an appropriate proportion of polyethylene glycol is introduced into the polyurethane segment, and the hard and soft segments in the polyurethane segment can form a more suitable The microphase separation structure increases the content force of the rigid segment, thereby improving the tensile strength and elongation of the film. In addition, the introduction of fluorine-containing polyols is end-capped with fluorine to obtain double cross-linked polyurethane, which endows the film with excellent optical transparency and flexibility due to the good compatibility of the fluorine-containing polyol with the polyurethane segment and the small roughness of the film. and the introduction of fluorine as a hydrophobic segment, endows the film with better self-cleaning and anti-adhesion properties.
此外,本发明引入改性氧化石墨烯对聚氨酯进行改性,能够与多元醇及异氰酸酯发生反应,可以充当TPU的硬段部分,使分子间形成部分化学交联结构,提高了材料的力学性能。引入改性多孔二氧化硅,由于多孔二氧化硅材料表面含有大量羟基可形成氢键,或者产生范德华力。在TPU体系中起到吸附作用的正是硅醇上的羟基,其构成了吸附中心。这些吸附剂具有巨大的表面积和孔体积,因此具有良好的吸附极性杂质的能力,改性聚氨酯体系中的金属离子可在吸附剂表面,从而进一步提高TPU薄膜的透光性。In addition, the present invention introduces modified graphene oxide to modify the polyurethane, which can react with polyols and isocyanates, and can act as the hard segment of TPU, so that a part of chemical cross-linking structure is formed between molecules, and the mechanical properties of the material are improved. The introduction of modified porous silica can form hydrogen bonds or generate van der Waals forces due to the presence of a large number of hydroxyl groups on the surface of porous silica materials. It is the hydroxyl group on silanol that plays an adsorption role in the TPU system, which constitutes the adsorption center. These adsorbents have a huge surface area and pore volume, so they have a good ability to adsorb polar impurities, and the metal ions in the modified polyurethane system can be on the surface of the adsorbent, thereby further improving the light transmittance of the TPU film.
在本发明中,聚酯多元醇的重量份数为45-55份,例如可以是45份、46份、47份、48份、49份、50份、51份、52份、53份、54份、55份等。In the present invention, the weight part of polyester polyol is 45-55 parts, for example, it can be 45 parts, 46 parts, 47 parts, 48 parts, 49 parts, 50 parts, 51 parts, 52 parts, 53 parts, 54 parts servings, 55 servings, etc.
在本发明中,聚乙二醇的重量份数为3-10份,例如可以是3份、4份、5份、6份、7份、8份、9份、10份等。In the present invention, the weight part of polyethylene glycol is 3-10 parts, for example, it can be 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, etc.
在本发明中,含氟多元醇的重量份数为1-5份,例如可以是1份、1.5份、2份、2.5份、3份、3.5份、4份、4.5份、5份等。In the present invention, the weight part of the fluorine-containing polyol is 1-5 parts, for example, 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, etc.
在本发明中,异佛尔酮二异氰酸酯的重量份数为25-35份,例如可以是25份、26份、27份、28份、29份、30份、31份、32份、33份、34份、35份等。In the present invention, the weight part of isophorone diisocyanate is 25-35 parts, for example, it can be 25 parts, 26 parts, 27 parts, 28 parts, 29 parts, 30 parts, 31 parts, 32 parts, 33 parts , 34 copies, 35 copies, etc.
在本发明中,扩链剂的重量份数为5-10份,例如可以是5份、5.5份、6份、6.5份、7份、7.5份、8份、8.5份、9份、9.5份、10份等。In the present invention, the weight part of the chain extender is 5-10 parts, for example, it can be 5 parts, 5.5 parts, 6 parts, 6.5 parts, 7 parts, 7.5 parts, 8 parts, 8.5 parts, 9 parts, 9.5 parts , 10 copies, etc.
在本发明中,改性氧化石墨烯的重量份数为1-5份,例如可以是1份、1.5份、2份、2.5份、3份、3.5份、4份、4.5份、5份等。In the present invention, the parts by weight of modified graphene oxide are 1-5 parts, such as 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, etc. .
在本发明中,催化剂的重量份数为0.1-0.5份,例如可以是0.1份、0.2份、0.3份、0.4份、0.5份等。In the present invention, the weight part of the catalyst is 0.1-0.5 part, for example, it can be 0.1 part, 0.2 part, 0.3 part, 0.4 part, 0.5 part, etc.
优选地,所述聚酯多元醇包括聚丁二酸丁二醇酯、聚己二酸丁二醇酯、聚己二酸己二醇酯或聚己二酸丁二醇乙二醇酯中的任意一种或至少两种的组合。Preferably, the polyester polyol comprises polybutylene succinate, polybutylene adipate, polyhexamethylene adipate or polybutylene ethylene adipate. Any one or a combination of at least two.
优选地,所述聚酯多元醇的数均分子量为1000-3000,例如可以是1000、1200、1400、1600、1800、2000、2200、2400、2600、2800、3000等。Preferably, the number average molecular weight of the polyester polyol is 1000-3000, for example, it can be 1000, 1200, 1400, 1600, 1800, 2000, 2200, 2400, 2600, 2800, 3000 and the like.
优选地,所述聚乙二醇的数均分子量为400-2000,例如可以是400、600、8000、1000、1200、1400、1600、1800、2000等。Preferably, the number average molecular weight of the polyethylene glycol is 400-2000, for example, it can be 400, 600, 8000, 1000, 1200, 1400, 1600, 1800, 2000 and the like.
优选地,所述含氟多元醇包括全氟聚醚醇、十三氟正辛醇、六氟正丙醇、六氟异丙醇或六氟正丁醇中的任意一种或至少两种的组合,优选为十三氟正辛醇和/或六氟正丁醇。Preferably, the fluorine-containing polyol comprises any one or at least two of perfluoropolyether alcohol, tridecafluoro-n-octanol, hexafluoro-n-propanol, hexafluoroisopropanol or hexafluoro-n-butanol combination, preferably tridecafluoro-n-octanol and/or hexafluoro-n-butanol.
优选地,所述扩链剂包括乙二醇、1,3-丙二醇、1,4-丁二醇或1,3-己二醇中的任意一种或至少两种的组合。Preferably, the chain extender includes any one or a combination of at least two of ethylene glycol, 1,3-propanediol, 1,4-butanediol or 1,3-hexanediol.
优选地,所述改性氧化石墨烯为壳聚糖改性氧化石墨烯。Preferably, the modified graphene oxide is chitosan modified graphene oxide.
本发明中,所述壳聚糖改性氧化石墨烯的制备方法为:将氧化石墨烯分散在溶剂(如THF、DMF等)中后,加入壳聚糖后,超声分散后,室温反应10h以上即可得到所述壳聚糖改性氧化石墨烯。采用壳聚糖改性氧化石墨烯得到壳聚糖-氧化石墨烯,壳聚糖含有大量的氨基和羟基,可以与氧化石墨烯产生强烈的氢键作用,氢键的存在可以使较薄的氧化石墨烯片层部分堆叠在壳聚糖表面从而形成大尺寸的褶皱状物质,能对聚合物分子的移动性施加强烈的几何约束,与聚合物链之间产生机械互锁,使得TPU复合材料交联程度提高,提高了拉伸 过程中材料的抗形变能。In the present invention, the preparation method of the chitosan-modified graphene oxide is as follows: after the graphene oxide is dispersed in a solvent (such as THF, DMF, etc.), after adding chitosan, after ultrasonic dispersion, react at room temperature for more than 10 hours The chitosan-modified graphene oxide can be obtained. Chitosan-graphene oxide is obtained by modifying graphene oxide with chitosan. Chitosan contains a large number of amino groups and hydroxyl groups, which can produce strong hydrogen bonds with graphene oxide. The existence of hydrogen bonds can make thinner oxidized Graphene sheets are partially stacked on the surface of chitosan to form large-scale folded substances, which can impose strong geometric constraints on the mobility of polymer molecules and mechanically interlock with polymer chains, making the TPU composite material. The degree of bonding is increased, and the deformation resistance of the material during the stretching process is improved.
优选地,所述改性多孔二氧化硅的制备原料按重量份数计包括:二氧化硅100份、氨水1-5份、表面活性剂1-5份、硅烷偶联剂0.5-2份和溶剂50-60份。Preferably, the raw materials for the preparation of the modified porous silica include in parts by weight: 100 parts of silica, 1-5 parts of ammonia water, 1-5 parts of surfactant, 0.5-2 parts of silane coupling agent and 50-60 parts of solvent.
在所述改性多孔二氧化硅的制备原料中,氨水的重量份数为1-5份,例如可以是1份、1.5份、2份、2.5份、3份、3.5份、4份、4.5份、5份等。In the raw materials for the preparation of the modified porous silica, the weight fraction of ammonia water is 1-5 parts, for example, it can be 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts servings, 5 servings, etc.
在所述改性多孔二氧化硅的制备原料中,表面活性剂的重量份数为1-5份,例如可以是1份、1.5份、2份、2.5份、3份、3.5份、4份、4.5份、5份等。In the preparation raw materials of the modified porous silica, the weight part of the surfactant is 1-5 parts, for example, it can be 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts , 4.5 copies, 5 copies, etc.
在所述改性多孔二氧化硅的制备原料中,硅烷偶联剂的重量份数为0.5-2份,例如可以是0.5份、0.6份、0.7份、0.8份、0.9份、1份、1.2份、1.4份、1.6份、1.8份、2份等。In the preparation raw materials of the modified porous silica, the weight part of the silane coupling agent is 0.5-2 parts, for example, it can be 0.5 part, 0.6 part, 0.7 part, 0.8 part, 0.9 part, 1 part, 1.2 part servings, 1.4 servings, 1.6 servings, 1.8 servings, 2 servings, etc.
在所述改性多孔二氧化硅的制备原料中,溶剂的重量份数为50-60份,例如可以是50份、51份、52份、53份、54份、55份、56份、57份、58份、59份、60份等。In the raw materials for the preparation of the modified porous silica, the weight of the solvent is 50-60 parts, such as 50 parts, 51 parts, 52 parts, 53 parts, 54 parts, 55 parts, 56 parts, 57 parts 58, 59, 60, etc.
优选地,所述表面活性剂为阳离子型表面活性剂,优选为十二烷基三甲基溴化铵、十六烷基三甲基溴化铵或十八烷基三甲基溴化铵中的任意一种或至少两种的组合。Preferably, the surfactant is a cationic surfactant, preferably one of dodecyltrimethylammonium bromide, cetyltrimethylammonium bromide or octadecyltrimethylammonium bromide any one or a combination of at least two.
优选地,所述硅烷偶联剂为含环氧基基团的硅烷偶联剂,优选为γ-缩水甘油氧基丙基三甲氧基硅烷。Preferably, the silane coupling agent is an epoxy group-containing silane coupling agent, preferably γ-glycidoxypropyltrimethoxysilane.
优选地,所述溶剂为THF和/或DMF。Preferably, the solvent is THF and/or DMF.
优选地,所述改性多孔二氧化硅由以下制备方法制备得到:将二氧化硅、氨水和溶剂混合,进行预热反应后,再加入阳离子型表面活性剂和硅烷偶联剂混合搅拌,得到所述改性多孔二氧化硅。Preferably, the modified porous silica is prepared by the following preparation method: mixing silica, ammonia water and a solvent, performing a preheating reaction, then adding a cationic surfactant and a silane coupling agent, mixing and stirring, to obtain The modified porous silica.
优选地,所述预热反应的温度为120-130℃,例如可以是120℃、122℃、 124℃、126℃、128℃、130℃等,所述预热反应的时间为1-2h,例如可以是1h、1.2h、1.4h、1.6h、1.8h、2h等。Preferably, the temperature of the preheating reaction is 120-130°C, such as 120°C, 122°C, 124°C, 126°C, 128°C, 130°C, etc., and the time of the preheating reaction is 1-2h, For example, it can be 1h, 1.2h, 1.4h, 1.6h, 1.8h, 2h and so on.
优选地,所述混合搅拌的温度为140-160℃,例如可以是140℃、142℃、146℃、148℃、150℃、152℃、154℃、156℃、158℃、160℃等,所述混合搅拌的时间为40-50min,例如可以是40min、42min、44min、46min、48min、50min等。Preferably, the temperature of the mixing and stirring is 140-160°C, such as 140°C, 142°C, 146°C, 148°C, 150°C, 152°C, 154°C, 156°C, 158°C, 160°C, etc. The mixing and stirring time is 40-50min, such as 40min, 42min, 44min, 46min, 48min, 50min, etc.
优选地,所述改性多孔二氧化硅的比表面积为600-800m 2/g,例如可以是600m 2/g、620m 2/g、640m 2/g、660m 2/g、680m 2/g、700m 2/g、720m 2/g、740m 2/g、760m 2/g、780m 2/g、800m 2/g等,所述改性多孔二氧化硅的的孔道的平均孔径为30-50nm,例如可以是30nm、32nm、34nm、36nm、38nm、40nm、42nm、44nm、46nm、48nm、50nm等。 Preferably, the specific surface area of the modified porous silica is 600-800 m 2 /g, such as 600 m 2 /g, 620 m 2 /g, 640 m 2 /g, 660 m 2 /g, 680 m 2 /g, 700m 2 /g, 720m 2 /g, 740m 2 /g, 760m 2 /g, 780m 2 /g, 800m 2 /g, etc., the average pore diameter of the pores of the modified porous silica is 30-50nm, For example, it can be 30 nm, 32 nm, 34 nm, 36 nm, 38 nm, 40 nm, 42 nm, 44 nm, 46 nm, 48 nm, 50 nm and the like.
优选地,所述催化剂包括二月桂酸二丁基锡、辛酸亚锡或辛酸钴中的任意一种或至少两种的组合。Preferably, the catalyst comprises any one or a combination of at least two of dibutyltin dilaurate, stannous octoate or cobalt octoate.
第二方面,本发明提供一种如第一方面所述电子产品用高透明TPU薄膜的制备方法,所述制备方法包括以下步骤:In the second aspect, the present invention provides a preparation method of the high-transparency TPU film for electronic products as described in the first aspect, the preparation method comprising the following steps:
(1)将聚酯多元醇、聚乙二醇、含氟多元醇、异佛尔酮二异氰酸酯和催化剂混合,反应得到聚氨酯预聚物;(1) mixing polyester polyol, polyethylene glycol, fluorine-containing polyol, isophorone diisocyanate and a catalyst, and reacting to obtain a polyurethane prepolymer;
(2)将步骤(1)得到的聚氨酯预聚物、改性氧化石墨烯和扩链剂混合,反应得到聚氨酯弹性体;(2) mixing the polyurethane prepolymer obtained in step (1), modified graphene oxide and chain extender, and reacting to obtain a polyurethane elastomer;
(3)将步骤(2)得到的聚氨酯弹性体和改性多孔二氧化硅混合搅拌,挤出成型,得到所述电子产品用高透明TPU薄膜。(3) mixing and stirring the polyurethane elastomer obtained in step (2) and the modified porous silica, and extrusion molding to obtain the high-transparency TPU film for electronic products.
优选地,步骤(1)所述反应的温度为80-120℃,例如可以是80℃、90℃、100℃、110℃、120℃等,所述反应的时间为2-4h,例如可以是2h、2.5h、3h、 3.5h、4h等。Preferably, the temperature of the reaction in step (1) is 80-120°C, such as 80°C, 90°C, 100°C, 110°C, 120°C, etc., and the reaction time is 2-4h, for example, it can be 2h, 2.5h, 3h, 3.5h, 4h, etc.
优选地,步骤(2)所述反应的温度为70-80℃,例如可以是70℃、72℃、74℃、76℃、78℃、80℃等,所述反应的时间为2-4h,例如可以是2h、2.5h、3h、3.5h、4h等。Preferably, the temperature of the reaction in step (2) is 70-80°C, such as 70°C, 72°C, 74°C, 76°C, 78°C, 80°C, etc., and the reaction time is 2-4h, For example, it can be 2h, 2.5h, 3h, 3.5h, 4h and so on.
优选地,步骤(3)所述混合搅拌的温度为50-60℃,例如可以是50℃、52℃、54℃、56℃、58℃、60℃等,所述混合搅拌的时间为20-30min,例如可以是20min、22min、24min、26min、28min、30min等。Preferably, the temperature of the mixing and stirring in step (3) is 50-60°C, for example, it can be 50°C, 52°C, 54°C, 56°C, 58°C, 60°C, etc., and the mixing and stirring time is 20- 30min, for example, can be 20min, 22min, 24min, 26min, 28min, 30min and the like.
优选地,步骤(3)所述挤出成型采用双螺杆挤出机进行,所述双螺杆挤出机的混合段温度为160-170℃,例如可以是160℃、162℃、164℃、166℃、168℃、170℃等,所述双螺杆挤出机的挤出段温度为170-180℃,例如可以是170℃、172℃、174℃、176℃、178℃、180℃等,所述双螺杆挤出机的机头温度为160-170℃,例如可以是160℃、162℃、164℃、166℃、168℃、170℃等。Preferably, the extrusion molding in step (3) is performed with a twin-screw extruder, and the temperature of the mixing section of the twin-screw extruder is 160-170°C, for example, 160°C, 162°C, 164°C, 166°C °C, 168 °C, 170 °C, etc., the temperature of the extrusion section of the twin-screw extruder is 170-180 °C, for example, it can be 170 °C, 172 °C, 174 °C, 176 °C, 178 °C, 180 °C, etc., so The temperature of the die head of the twin-screw extruder is 160-170°C, such as 160°C, 162°C, 164°C, 166°C, 168°C, 170°C, and the like.
优选地,所述电子产品用高透明TPU薄膜的制备方法包括以下步骤:Preferably, the preparation method of the highly transparent TPU film for electronic products comprises the following steps:
(1)将聚酯多元醇、聚乙二醇、含氟多元醇、异佛尔酮二异氰酸酯和催化剂混合,在80-120℃下反应2-4h,得到聚氨酯预聚物;(1) mixing polyester polyol, polyethylene glycol, fluorine-containing polyol, isophorone diisocyanate and a catalyst, and reacting at 80-120° C. for 2-4 hours to obtain a polyurethane prepolymer;
(2)将步骤(1)得到的聚氨酯预聚物、改性氧化石墨烯和扩链剂混合,在70-80℃下反应2-4h,得到聚氨酯弹性体;(2) mixing the polyurethane prepolymer obtained in step (1), the modified graphene oxide and the chain extender, and reacting at 70-80° C. for 2-4 hours to obtain a polyurethane elastomer;
(3)将步骤(2)得到的聚氨酯弹性体和改性多孔二氧化硅在50-60℃混合搅拌20-30min,采用双螺杆挤出机挤出,所述双螺杆挤出机的混合段温度为160-170℃,所述双螺杆挤出机的挤出段温度为170-180℃,所述双螺杆挤出机的机头温度为160-170℃,再利用单螺杆挤出流延成膜或吹塑成膜,得到所述电子产品用高透明TPU薄膜。(3) The polyurethane elastomer obtained in step (2) and the modified porous silica are mixed and stirred at 50-60° C. for 20-30 minutes, and extruded by a twin-screw extruder. The mixing section of the twin-screw extruder The temperature is 160-170°C, the temperature of the extrusion section of the twin-screw extruder is 170-180°C, and the temperature of the head of the twin-screw extruder is 160-170°C, and then the single-screw extruder is used for extrusion casting. Film-forming or blow-molding film-forming to obtain the high-transparency TPU film for electronic products.
相对于现有技术,本发明具有以下有益效果:Compared with the prior art, the present invention has the following beneficial effects:
(1)本发明所述TPU薄膜材料由适当比例的聚酯多元醇、聚乙二醇、含氟多元醇、异佛尔酮二异氰酸酯、扩链剂、改性氧化石墨烯、改性多孔二氧化硅和催化剂制备得到,在保证TPU薄膜材料具有优异的透明度的基础上,还具有较小的粗糙度和优良的力学性能,更适用于电子产品的防护。(1) The TPU film material of the present invention is composed of polyester polyol, polyethylene glycol, fluorine-containing polyol, isophorone diisocyanate, chain extender, modified graphene oxide, modified porous diisocyanate in appropriate proportions. The silicon oxide and the catalyst are prepared, and on the basis of ensuring the excellent transparency of the TPU film material, it also has small roughness and excellent mechanical properties, and is more suitable for the protection of electronic products.
(2)本发明所述TPU薄膜材料的透光率在97%以上,粗糙度在5nm以下,拉伸强度在60-70MPa以上,断裂伸长率为800-1000%。(2) The light transmittance of the TPU film material of the present invention is above 97%, the roughness is below 5nm, the tensile strength is above 60-70MPa, and the elongation at break is 800-1000%.
具体实施方式detailed description
下面通过具体实施方式来进一步说明本发明的技术方案。本领域技术人员应该明了,所述实施例仅仅是帮助理解本发明,不应视为对本发明的具体限制。The technical solutions of the present invention are further described below through specific embodiments. It should be understood by those skilled in the art that the embodiments are only for helping the understanding of the present invention, and should not be regarded as a specific limitation of the present invention.
制备例1Preparation Example 1
本制备例提供一种改性多孔二氧化硅I,所述改性多孔二氧化硅I由以下制备方法制备得到:将100g的二氧化硅、3g 25wt%的氨水和50g的THF混合,在120℃预热反应2h后,再加入2g的十六烷基三甲基溴化铵和1g的γ-缩水甘油氧基丙基三甲氧基硅烷,在150℃下混合搅拌45min,得到比表面积为750m 2/g,平均孔径为45nm的改性多孔二氧化硅I。 This preparation example provides a modified porous silica I, which is prepared by the following preparation method: 100 g of silica, 3 g of 25 wt % ammonia water and 50 g of THF are mixed, and the mixture is mixed at 120 After preheating the reaction for 2 hours, 2g of cetyltrimethylammonium bromide and 1g of γ-glycidyloxypropyltrimethoxysilane were added, and the mixture was mixed and stirred at 150°C for 45min to obtain a specific surface area of 750m 2 /g, modified porous silica I with an average pore size of 45 nm.
制备例2Preparation Example 2
本制备例提供一种改性多孔二氧化硅II,所述改性多孔二氧化硅II由以下制备方法制备得到:将100g的二氧化硅、2g 25wt%的氨水和60g的THF混合,在130℃预热反应1h后,再加入3g的十二烷基三甲基溴化铵和1g的γ-缩水甘油氧基丙基三甲氧基硅烷,在150℃下混合搅拌45min,得到比表面积为730m 2/g,平均孔径为42nm的改性多孔二氧化硅II。 This preparation example provides a modified porous silica II. The modified porous silica II is prepared by the following preparation method: 100 g of silica, 2 g of 25 wt % ammonia water and 60 g of THF are mixed at 130 After preheating the reaction for 1 h, 3 g of dodecyl trimethyl ammonium bromide and 1 g of γ-glycidyloxypropyltrimethoxysilane were added, and the mixture was mixed and stirred at 150 ° C for 45 min to obtain a specific surface area of 730 m 2 /g, modified porous silica II with an average pore size of 42 nm.
制备例3Preparation Example 3
本制备例提供一种改性多孔二氧化硅III,所述改性多孔二氧化硅III由以下制备方法制备得到:将100g的二氧化硅、4g 25wt%的氨水和60g的THF混合,在120℃预热反应1h后,再加入2g的十八烷基三甲基溴化铵和1g的γ-缩水甘油氧基丙基三甲氧基硅烷,在150℃下混合搅拌45min,得到比表面积为690m 2/g,平均孔径为38nm的改性多孔二氧化硅III。 This preparation example provides a modified porous silica III. The modified porous silica III is prepared by the following preparation method: 100 g of silica, 4 g of 25 wt% ammonia water and 60 g of THF are mixed at 120 After preheating the reaction for 1 h, 2 g of octadecyltrimethylammonium bromide and 1 g of γ-glycidyloxypropyltrimethoxysilane were added, and the mixture was mixed and stirred at 150 °C for 45 minutes to obtain a specific surface area of 690 m 2 /g, modified porous silica III with an average pore size of 38 nm.
制备例4Preparation Example 4
本制备例提供一种改性多孔二氧化硅IV,所述改性多孔二氧化硅IV由以下制备方法制备得到:将100g的二氧化硅、3g 25wt%的氨水和50g的THF混合,在120℃预热反应2h后,再加入2g的十二烷基苯磺酸钠和1g的γ-缩水甘油氧基丙基三甲氧基硅烷,在150℃下混合搅拌45min,得到比表面积为620m 2/g,平均孔径为33nm的改性多孔二氧化硅IV。 This preparation example provides a modified porous silica IV, and the modified porous silica IV is prepared by the following preparation method: 100 g of silica, 3 g of 25 wt % ammonia water and 50 g of THF are mixed, and the mixture is mixed at 120 After preheating the reaction at ℃ for 2h, add 2g of sodium dodecylbenzenesulfonate and 1g of γ-glycidyloxypropyltrimethoxysilane, mix and stir at 150℃ for 45min, to obtain a specific surface area of 620m 2 / g, Modified porous silica IV with an average pore size of 33 nm.
制备例5Preparation Example 5
本制备例提供一种改性多孔二氧化硅V,所述改性多孔二氧化硅V由以下制备方法制备得到:将100g的二氧化硅、3g 25wt%的氨水和50g的THF混合,在120℃预热反应2h后,再加入1g的γ-缩水甘油氧基丙基三甲氧基硅烷,在150℃下混合搅拌45min,得到比表面积为580m 2/g,平均孔径为28nm的改性多孔二氧化硅V。 This preparation example provides a modified porous silica V, the modified porous silica V is prepared by the following preparation method: 100 g of silica, 3 g of 25wt% ammonia water and 50 g of THF are mixed, After preheating the reaction for 2 hours at ℃, 1 g of γ-glycidyloxypropyltrimethoxysilane was added, and the mixture was mixed and stirred at 150 ℃ for 45 minutes to obtain a modified porous bilayer with a specific surface area of 580 m 2 /g and an average pore diameter of 28 nm. Silicon oxide V.
制备例6Preparation Example 6
本制备例提供一种壳聚糖改性氧化石墨烯,所述壳聚糖改性氧化石墨烯由以下制备方法制备得到:将100g的氧化石墨烯分散于50mL的THF中,加入10g壳聚糖,进行超声分散,超声功率为600W,以200r/min的速度在25℃下搅拌12h进行接枝反应,得到壳聚糖改性氧化石墨烯分散液,浓缩后干燥,得到壳聚糖改性氧化石墨烯。This preparation example provides a chitosan-modified graphene oxide, and the chitosan-modified graphene oxide is prepared by the following preparation method: disperse 100 g of graphene oxide in 50 mL of THF, add 10 g of chitosan , ultrasonic dispersion was carried out, the ultrasonic power was 600W, and the grafting reaction was carried out by stirring at 200 r/min at 25 °C for 12 h to obtain a chitosan modified graphene oxide dispersion, which was concentrated and dried to obtain a chitosan modified oxidation solution. Graphene.
实施例1Example 1
本实施例提供一种电子产品用高透明TPU薄膜,所述电子产品用高透明TPU薄膜的制备原料按重量份数计包括如下组分:The present embodiment provides a high-transparency TPU film for electronic products, and the preparation raw materials of the high-transparency TPU film for electronic products include the following components in parts by weight:
Figure PCTCN2020140449-appb-000002
Figure PCTCN2020140449-appb-000002
其中,聚己二酸丁二醇酯的数均分子量为2000,聚乙二醇的数均分子量为800,改性多孔二氧化硅为制备例1提供的改性多孔二氧化硅I。Wherein, the number-average molecular weight of polybutylene adipate is 2000, the number-average molecular weight of polyethylene glycol is 800, and the modified porous silica is modified porous silica I provided in Preparation Example 1.
本实施例所述电子产品用高透明TPU薄膜的制备方法包括以下步骤:The preparation method of the high-transparency TPU film for electronic products described in this embodiment comprises the following steps:
(1)将聚己二酸丁二醇酯、聚乙二醇、十三氟正辛醇、异佛尔酮二异氰酸酯和二月桂酸二丁基锡混合,在100℃下反应3h,得到聚氨酯预聚物;(1) Mix polybutylene adipate, polyethylene glycol, tridecafluoro-n-octanol, isophorone diisocyanate and dibutyltin dilaurate, and react at 100° C. for 3 hours to obtain a polyurethane prepolymer thing;
(2)将步骤(1)得到的聚氨酯预聚物、壳聚糖改性氧化石墨烯和乙二醇混合,在75℃下反应3h,得到聚氨酯弹性体;(2) mixing the polyurethane prepolymer obtained in step (1), chitosan-modified graphene oxide and ethylene glycol, and reacting at 75° C. for 3 hours to obtain a polyurethane elastomer;
(3)将步骤(2)得到的聚氨酯弹性体和改性多孔二氧化硅I在50℃混合搅拌30min,采用双螺杆挤出机挤出,所述双螺杆挤出机的混合段温度为160℃,所述双螺杆挤出机的挤出段温度为180℃,所述双螺杆挤出机的机头温度为160℃,再利用单螺杆挤出流延成膜,得到所述电子产品用高透明TPU薄膜。(3) The polyurethane elastomer obtained in step (2) and the modified porous silica I were mixed and stirred at 50° C. for 30 min, and extruded by a twin-screw extruder, and the temperature of the mixing section of the twin-screw extruder was 160°C °C, the temperature of the extrusion section of the twin-screw extruder is 180 °C, and the temperature of the head of the twin-screw extruder is 160 °C, and then the single-screw extrusion is used to cast a film to obtain the electronic product. High transparent TPU film.
实施例2Example 2
本实施例提供一种电子产品用高透明TPU薄膜,所述电子产品用高透明TPU薄膜的制备原料按重量份数计包括如下组分:The present embodiment provides a high-transparency TPU film for electronic products, and the preparation raw materials of the high-transparency TPU film for electronic products include the following components in parts by weight:
Figure PCTCN2020140449-appb-000003
Figure PCTCN2020140449-appb-000003
其中,聚己二酸丁二醇酯的数均分子量为1000,聚乙二醇的数均分子量为1000,改性多孔二氧化硅为制备例2提供的改性多孔二氧化硅II。The number average molecular weight of polybutylene adipate is 1000, the number average molecular weight of polyethylene glycol is 1000, and the modified porous silica is modified porous silica II provided in Preparation Example 2.
本实施例所述电子产品用高透明TPU薄膜的制备方法包括以下步骤:The preparation method of the high-transparency TPU film for electronic products described in this embodiment comprises the following steps:
(1)将聚己二酸丁二醇酯、聚乙二醇、六氟正丁醇、异佛尔酮二异氰酸酯和辛酸亚锡混合,在100℃下反应3h,得到聚氨酯预聚物;(1) mixing polybutylene adipate, polyethylene glycol, hexafluoro-n-butanol, isophorone diisocyanate and stannous octoate, and reacting at 100° C. for 3 hours to obtain a polyurethane prepolymer;
(2)将步骤(1)得到的聚氨酯预聚物、壳聚糖改性氧化石墨烯和乙二醇混合,在75℃下反应3h,得到聚氨酯弹性体;(2) mixing the polyurethane prepolymer obtained in step (1), chitosan-modified graphene oxide and ethylene glycol, and reacting at 75° C. for 3 hours to obtain a polyurethane elastomer;
(3)将步骤(2)得到的聚氨酯弹性体和改性多孔二氧化硅II在50℃混合搅拌30min,采用双螺杆挤出机挤出,所述双螺杆挤出机的混合段温度为170℃,所述双螺杆挤出机的挤出段温度为180℃,所述双螺杆挤出机的机头温度为160℃,再利用单螺杆挤出流延成膜,得到所述电子产品用高透明TPU薄膜。(3) The polyurethane elastomer obtained in step (2) and the modified porous silica II were mixed and stirred at 50° C. for 30 minutes, and extruded by a twin-screw extruder, and the temperature of the mixing section of the twin-screw extruder was 170° C. °C, the temperature of the extrusion section of the twin-screw extruder is 180 °C, and the temperature of the head of the twin-screw extruder is 160 °C, and then the single-screw extrusion is used to cast a film to obtain the electronic product. High transparent TPU film.
实施例3Example 3
本实施例提供一种电子产品用高透明TPU薄膜,所述电子产品用高透明 TPU薄膜的制备原料按重量份数计包括如下组分:The present embodiment provides a high-transparency TPU film for electronic products, and the preparation raw materials of the high-transparency TPU film for electronic products include the following components in parts by weight:
Figure PCTCN2020140449-appb-000004
Figure PCTCN2020140449-appb-000004
其中,聚己二酸丁二醇酯的数均分子量为2000,聚乙二醇的数均分子量为600,改性多孔二氧化硅为制备例3提供的改性多孔二氧化硅III。The number average molecular weight of polybutylene adipate is 2000, the number average molecular weight of polyethylene glycol is 600, and the modified porous silica is modified porous silica III provided in Preparation Example 3.
本实施例所述电子产品用高透明TPU薄膜的制备方法包括以下步骤:The preparation method of the high-transparency TPU film for electronic products described in this embodiment comprises the following steps:
(1)将聚己二酸丁二醇酯、聚乙二醇、六氟正丁醇、异佛尔酮二异氰酸酯和辛酸亚锡混合,在100℃下反应3h,得到聚氨酯预聚物;(1) mixing polybutylene adipate, polyethylene glycol, hexafluoro-n-butanol, isophorone diisocyanate and stannous octoate, and reacting at 100° C. for 3 hours to obtain a polyurethane prepolymer;
(2)将步骤(1)得到的聚氨酯预聚物、壳聚糖改性氧化石墨烯和乙二醇混合,在75℃下反应3h,得到聚氨酯弹性体;(2) mixing the polyurethane prepolymer obtained in step (1), chitosan-modified graphene oxide and ethylene glycol, and reacting at 75° C. for 3 hours to obtain a polyurethane elastomer;
(3)将步骤(2)得到的聚氨酯弹性体和改性多孔二氧化硅III在50℃混合搅拌30min,采用双螺杆挤出机挤出,所述双螺杆挤出机的混合段温度为170℃,所述双螺杆挤出机的挤出段温度为180℃,所述双螺杆挤出机的机头温度为160℃,再利用单螺杆挤出流延成膜,得到所述电子产品用高透明TPU薄膜。(3) The polyurethane elastomer obtained in step (2) and the modified porous silica III were mixed and stirred at 50° C. for 30 minutes, and extruded by a twin-screw extruder. The temperature of the mixing section of the twin-screw extruder was 170 °C, the temperature of the extrusion section of the twin-screw extruder is 180 °C, and the temperature of the head of the twin-screw extruder is 160 °C, and then the single-screw extrusion is used to cast a film to obtain the electronic product. High transparent TPU film.
实施例4Example 4
本实施例提供一种电子产品用高透明TPU薄膜,与实施例1的区别仅在于, 将改性多孔二氧化硅I替换为等质量的六改性多孔二氧化硅IV,其他组分含量及制备方法同实施例1。This embodiment provides a high-transparency TPU film for electronic products. The only difference from Embodiment 1 is that the modified porous silica I is replaced with an equivalent mass of six-modified porous silica IV, and the contents of other components and The preparation method is the same as in Example 1.
实施例5Example 5
本实施例提供一种电子产品用高透明TPU薄膜,与实施例1的区别仅在于,将改性多孔二氧化硅I替换为等质量的改性多孔二氧化硅V,其他组分含量及制备方法同实施例1。This embodiment provides a high-transparency TPU film for electronic products. The only difference from Embodiment 1 is that the modified porous silica I is replaced with the same quality of modified porous silica V, and the contents of other components and the preparation The method is the same as in Example 1.
实施例6Example 6
本实施例提供一种电子产品用高透明TPU薄膜,与实施例1的区别仅在于,将十三氟正辛醇替换为等质量的六氟异丙醇,其他组分含量及制备方法同实施例1。This embodiment provides a high-transparency TPU film for electronic products. The only difference from Embodiment 1 is that tridecafluoro-n-octanol is replaced with hexafluoroisopropanol of the same quality, and the contents and preparation methods of other components are the same as in the implementation. example 1.
实施例7Example 7
本实施例提供一种电子产品用高透明TPU薄膜,与实施例1的区别仅在于,所述聚乙二醇含量为1份,十三氟正辛醇含量为11份,其他组分含量及制备方法同实施例1。This embodiment provides a high-transparency TPU film for electronic products. The only difference from Embodiment 1 is that the content of polyethylene glycol is 1 part, the content of tridecafluoro-n-octanol is 11 parts, and the content of other components and The preparation method is the same as in Example 1.
实施例8Example 8
本实施例提供一种电子产品用高透明TPU薄膜,与实施例1的区别仅在于,所述聚乙二醇含量为11份,十三氟正辛醇含量为1份,其他组分含量及制备方法同实施例1。This embodiment provides a high-transparency TPU film for electronic products. The only difference from Embodiment 1 is that the content of polyethylene glycol is 11 parts, the content of tridecafluoro-n-octanol is 1 part, and the content of other components and The preparation method is the same as in Example 1.
对比例1Comparative Example 1
本对比例提供一种电子产品用高透明TPU薄膜,与实施例1的区别仅在于,不添加聚乙二醇,聚己二酸丁二醇酯含量增至58份,其他组分含量及制备方法同实施例1。This comparative example provides a high-transparency TPU film for electronic products. The only difference from Example 1 is that polyethylene glycol is not added, the content of polybutylene adipate is increased to 58 parts, and the content and preparation of other components The method is the same as in Example 1.
对比例2Comparative Example 2
本对比例提供一种电子产品用高透明TPU薄膜,与实施例1的区别仅在于,不添加十三氟正辛醇,聚己二酸丁二醇酯含量增至54份,其他组分含量及制备方法同实施例1。This comparative example provides a high-transparency TPU film for electronic products. The difference from Example 1 is that no tridecafluoro-n-octanol is added, the content of polybutylene adipate is increased to 54 parts, and the content of other components is And the preparation method is the same as Example 1.
对比例3Comparative Example 3
本对比例提供一种电子产品用高透明TPU薄膜,与实施例1的区别仅在于,将异佛尔酮二异氰酸酯替换为等质量的六亚甲基二异氰酸酯,其他组分含量及制备方法同实施例1。This comparative example provides a high-transparency TPU film for electronic products. The difference from Example 1 is that isophorone diisocyanate is replaced with hexamethylene diisocyanate of the same quality, and the contents and preparation methods of other components are the same Example 1.
对比例4Comparative Example 4
本对比例提供一种电子产品用高透明TPU薄膜,与实施例1的区别仅在于,不添加壳聚糖改性氧化石墨烯,将改性多孔二氧化硅含量增至5份,其他组分含量及制备方法同实施例1。This comparative example provides a highly transparent TPU film for electronic products. The only difference from Example 1 is that chitosan-modified graphene oxide is not added, the content of modified porous silica is increased to 5 parts, and other components The content and preparation method are the same as those in Example 1.
对比例5Comparative Example 5
本对比例提供一种电子产品用高透明TPU薄膜,与实施例1的区别仅在于,不添加改性多孔二氧化硅,将壳聚糖改性氧化石墨烯含量增至5份,其他组分含量及制备方法同实施例1。This comparative example provides a highly transparent TPU film for electronic products. The only difference from Example 1 is that no modified porous silica is added, the content of chitosan-modified graphene oxide is increased to 5 parts, and other components are The content and preparation method are the same as those in Example 1.
对比例6Comparative Example 6
本对比例提供一种电子产品用高透明TPU薄膜,与实施例1的区别仅在于,将改性氧化石墨烯替换为等质量的氧化石墨烯,其他组分含量及制备方法同实施例1。This comparative example provides a high-transparency TPU film for electronic products, and the difference from Example 1 is only that the modified graphene oxide is replaced with graphene oxide of equal quality, and the content of other components and the preparation method are the same as those of Example 1.
对比例7Comparative Example 7
本对比例提供一种电子产品用高透明TPU薄膜,与实施例1的区别仅在于,将改性多孔二氧化硅替换为等质量的二氧化硅,其他组分含量及制备方法同实施例1。This comparative example provides a high-transparency TPU film for electronic products. The only difference from Example 1 is that the modified porous silica is replaced with silica of equal quality, and the contents and preparation methods of other components are the same as those of Example 1. .
性能测试Performance Testing
对上述实施例1-8制备得到的电子产品用高透明TPU薄膜和对比例1-7制备得到的电子产品用高透明TPU薄膜进行各项性能测试。其中,透光率采用透光率测试标准GB/T 2410-2008进行,粗糙度采用德国Bruker公司的原子力显微镜进行测试,并根据GB/T1040.3-2006测试各薄膜材料的拉伸强度,根据GB/T 1040.1-2006测试各薄膜材料的断裂伸长率。Various performance tests were carried out on the high-transparency TPU films for electronic products prepared in the above examples 1-8 and the high-transparency TPU films for electronic products prepared in the comparative examples 1-7. Among them, the light transmittance is tested by the light transmittance test standard GB/T 2410-2008, the roughness is tested by the atomic force microscope of Bruker Company in Germany, and the tensile strength of each film material is tested according to GB/T1040.3-2006, according to GB/T 1040.1-2006 tests the elongation at break of each film material.
具体测试结果如下表1所示:The specific test results are shown in Table 1 below:
表1Table 1
项目project 透光率/%Transmittance/% 粗糙度/nmRoughness/nm 拉伸强度/MPaTensile strength/MPa 断裂伸长率%Elongation at break%
实施例1Example 1 99.599.5 3.93.9 6868 960960
实施例2Example 2 99.299.2 3.93.9 7070 980980
实施例3Example 3 99.599.5 4.04.0 6969 950950
实施例4Example 4 99.099.0 4.54.5 6666 920920
实施例5Example 5 97.597.5 4.54.5 6767 890890
实施例6Example 6 98.298.2 4.24.2 6565 850850
实施例7Example 7 98.098.0 4.64.6 6262 860860
实施例8Example 8 97.897.8 4.54.5 6363 840840
对比例1Comparative Example 1 91.591.5 6.86.8 5252 620620
对比例2Comparative Example 2 92.392.3 7.27.2 5151 730730
对比例3Comparative Example 3 90.590.5 6.56.5 4848 640640
对比例4Comparative Example 4 95.295.2 12.012.0 4646 650650
对比例5Comparative Example 5 89.989.9 8.28.2 4242 610610
对比例6Comparative Example 6 91.691.6 15.415.4 5252 700700
对比例7Comparative Example 7 86.786.7 16.816.8 5656 720720
由表1测试数据可知,本发明所述TPU薄膜材料的透光率在97%以上,粗糙度在5nm以下,拉伸强度在60-70MPa以上,断裂伸长率为800-1000%。说明本发明所述TPU薄膜材料由适当比例的聚酯多元醇、聚乙二醇、含氟多元醇、异佛尔酮二异氰酸酯、扩链剂、改性氧化石墨烯、改性多孔二氧化硅和催化剂制备得到,在保证TPU薄膜材料具有优异的透明度的基础上,还具有较小的粗糙度和优良的力学性能,更适用于电子产品的防护。It can be seen from the test data in Table 1 that the light transmittance of the TPU film material of the present invention is above 97%, the roughness is below 5nm, the tensile strength is above 60-70MPa, and the elongation at break is 800-1000%. Explain that the TPU film material of the present invention is composed of appropriate proportions of polyester polyol, polyethylene glycol, fluorine-containing polyol, isophorone diisocyanate, chain extender, modified graphene oxide, modified porous silica And the catalyst is prepared, on the basis of ensuring the excellent transparency of the TPU film material, it also has small roughness and excellent mechanical properties, and is more suitable for the protection of electronic products.
由实施例1和实施例4、5的对比可知,阳离子表面活性剂有助于形成高表面积高孔径的改性多孔二氧化硅,从而更可靠地吸附金属离子,以进一步提高薄膜的透光率,并降低其粗糙度。由实施例1和实施例7、8的对比可知,聚乙二醇和十三氟正辛醇的比例在本申请范围内时,制备得到的TPU薄膜材料具有更为优异的透明度和柔韧性及更小的粗糙度。From the comparison between Example 1 and Examples 4 and 5, it can be seen that the cationic surfactant helps to form modified porous silica with high surface area and high pore size, so as to more reliably adsorb metal ions to further improve the light transmittance of the film , and reduce its roughness. From the comparison of Example 1 and Examples 7 and 8, it can be seen that when the ratio of polyethylene glycol and tridecafluoro-n-octanol is within the scope of the application, the prepared TPU film material has more excellent transparency and flexibility and is more flexible. small roughness.
由实施例1和对比例1的对比可知,缺少聚乙二醇,则无法很好地增加刚性链段的含量作用力,因此薄膜的拉伸强度和伸长率下降明显。由实施例1和对比例2,缺少含氟多元醇,薄膜的光学透明度和柔韧性下降明显。由实施例1和对比例3的对比可知,异佛尔酮二异氰酸酯形成的膜更为透明,这是由于异佛尔酮二异氰酸酯分子不对称,不易形成结晶。由实施例1和对比例4-7的对比可知,不添加改性氧化石墨烯、改性多孔二氧化硅,或将二者替换为未经改性的氧化石墨烯和二氧化硅时,薄膜的光学透明度和柔韧性下降明显,且粗糙度明显上升。It can be seen from the comparison between Example 1 and Comparative Example 1 that, lack of polyethylene glycol, the content of the rigid segment cannot be well increased, so the tensile strength and elongation of the film decrease significantly. From Example 1 and Comparative Example 2, lack of fluorine-containing polyol, the optical transparency and flexibility of the film decreased significantly. It can be seen from the comparison between Example 1 and Comparative Example 3 that the film formed by isophorone diisocyanate is more transparent, because the isophorone diisocyanate molecule is asymmetric and difficult to form crystals. From the comparison of Example 1 and Comparative Examples 4-7, it can be seen that when the modified graphene oxide and modified porous silica are not added, or the two are replaced with unmodified graphene oxide and The optical transparency and flexibility decreased significantly, and the roughness increased significantly.
申请人声明,本发明通过上述实施例来说明所述电子产品用高透明TPU薄膜及其制备方法,但本发明并不局限于上述实施例,即不意味着本发明必须依赖上述实施例才能实施。所属技术领域的技术人员应该明了,对本发明的任何 改进,对本发明产品各原料的等效替换及辅助成分的添加、具体方式的选择等,均落在本发明的保护范围和公开范围之内。The applicant declares that the present invention describes the high-transparency TPU film for electronic products and its preparation method by the above-mentioned embodiments, but the present invention is not limited to the above-mentioned embodiments, that is to say, it does not mean that the present invention can only be implemented by relying on the above-mentioned embodiments. . Those skilled in the art should understand that any improvement of the present invention, the equivalent replacement of each raw material of the product of the present invention, the addition of auxiliary components, the selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims (10)

  1. 一种电子产品用高透明TPU薄膜,其特征在于,所述电子产品用高透明TPU薄膜的制备原料按重量份数计包括如下组分:A high-transparency TPU film for electronic products, characterized in that, the preparation raw materials of the high-transparency TPU film for electronic products include the following components in parts by weight:
    Figure PCTCN2020140449-appb-100001
    Figure PCTCN2020140449-appb-100001
  2. 根据权利要求1所述的电子产品用高透明TPU薄膜,其特征在于,所述聚酯多元醇包括聚丁二酸丁二醇酯、聚己二酸丁二醇酯、聚己二酸己二醇酯或聚己二酸丁二醇乙二醇酯中的任意一种或至少两种的组合;The highly transparent TPU film for electronic products according to claim 1, wherein the polyester polyol comprises polybutylene succinate, polybutylene adipate, polyhexamethylene adipate Any one or a combination of at least two alcohol esters or polybutylene adipate glycol esters;
    优选地,所述聚酯多元醇的数均分子量为1000-3000。Preferably, the number average molecular weight of the polyester polyol is 1000-3000.
  3. 根据权利要求1或2所述的电子产品用高透明TPU薄膜,其特征在于,所述聚乙二醇的数均分子量为400-2000;The high-transparency TPU film for electronic products according to claim 1 or 2, wherein the number-average molecular weight of the polyethylene glycol is 400-2000;
    优选地,所述含氟多元醇包括全氟聚醚醇、十三氟正辛醇、六氟正丙醇、六氟异丙醇或六氟正丁醇中的任意一种或至少两种的组合,优选为十三氟正辛醇和/或六氟正丁醇;Preferably, the fluorine-containing polyol comprises any one or at least two of perfluoropolyether alcohol, tridecafluoro-n-octanol, hexafluoro-n-propanol, hexafluoroisopropanol or hexafluoro-n-butanol combination, preferably tridecafluoro-n-octanol and/or hexafluoro-n-butanol;
    优选地,所述扩链剂包括乙二醇、1,3-丙二醇、1,4-丁二醇或1,3-己二醇中的任意一种或至少两种的组合。Preferably, the chain extender includes any one or a combination of at least two of ethylene glycol, 1,3-propanediol, 1,4-butanediol or 1,3-hexanediol.
  4. 根据权利要求1-3中任一项所述的电子产品用高透明TPU薄膜,其特征在于,所述改性氧化石墨烯为壳聚糖改性氧化石墨烯。The highly transparent TPU film for electronic products according to any one of claims 1-3, wherein the modified graphene oxide is chitosan modified graphene oxide.
  5. 根据权利要求1-4中任一项所述的电子产品用高透明TPU薄膜,其特征在于,所述改性多孔二氧化硅的制备原料按重量份数计包括:二氧化硅100份、氨水1-5份、表面活性剂1-5份、硅烷偶联剂0.5-2份和溶剂50-60份;The high-transparency TPU film for electronic products according to any one of claims 1-4, wherein the raw materials for preparing the modified porous silica include in parts by weight: 100 parts of silica, ammonia water 1-5 parts, 1-5 parts of surfactant, 0.5-2 parts of silane coupling agent and 50-60 parts of solvent;
    优选地,所述表面活性剂为阳离子型表面活性剂,优选为十二烷基三甲基溴化铵、十六烷基三甲基溴化铵或十八烷基三甲基溴化铵中的任意一种或至少两种的组合;Preferably, the surfactant is a cationic surfactant, preferably one of dodecyltrimethylammonium bromide, cetyltrimethylammonium bromide or octadecyltrimethylammonium bromide any one or a combination of at least two;
    优选地,所述硅烷偶联剂为含环氧基基团的硅烷偶联剂,优选为γ-缩水甘油氧基丙基三甲氧基硅烷;Preferably, the silane coupling agent is an epoxy group-containing silane coupling agent, preferably γ-glycidoxypropyltrimethoxysilane;
    优选地,所述溶剂为THF和/或DMF;Preferably, the solvent is THF and/or DMF;
    优选地,所述改性多孔二氧化硅由以下制备方法制备得到:将二氧化硅、氨水和溶剂混合,进行预热反应后,再加入阳离子型表面活性剂和硅烷偶联剂混合搅拌,得到所述改性多孔二氧化硅;Preferably, the modified porous silica is prepared by the following preparation method: mixing silica, ammonia water and a solvent, performing a preheating reaction, then adding a cationic surfactant and a silane coupling agent, mixing and stirring, to obtain the modified porous silica;
    优选地,所述预热反应的温度为120-130℃,所述预热反应的时间为1-2h;Preferably, the temperature of the preheating reaction is 120-130°C, and the time of the preheating reaction is 1-2h;
    优选地,所述混合搅拌的温度为140-160℃,所述混合搅拌的时间为40-50min;Preferably, the temperature of the mixing and stirring is 140-160° C., and the time of the mixing and stirring is 40-50 min;
    优选地,所述改性多孔二氧化硅的比表面积为600-800m 2/g,所述改性多孔二氧化硅的的孔道的平均孔径为30-50nm。 Preferably, the specific surface area of the modified porous silica is 600-800 m 2 /g, and the average pore diameter of the pores of the modified porous silica is 30-50 nm.
  6. 根据权利要求1-5中任一项所述的电子产品用高透明TPU薄膜,其特征在于,所述催化剂包括二月桂酸二丁基锡、辛酸亚锡或辛酸钴中的任意一种或至少两种的组合。The highly transparent TPU film for electronic products according to any one of claims 1-5, wherein the catalyst comprises any one or at least two of dibutyltin dilaurate, stannous octoate or cobalt octoate The combination.
  7. 根据权利要求1-6中任一项所述电子产品用高透明TPU薄膜的制备方法,其特征在于,所述制备方法包括以下步骤:According to the preparation method of the high-transparency TPU film for electronic products according to any one of claims 1-6, the preparation method comprises the following steps:
    (1)将聚酯多元醇、聚乙二醇、含氟多元醇、异佛尔酮二异氰酸酯和催化 剂混合,反应得到聚氨酯预聚物;(1) polyester polyol, polyethylene glycol, fluorine-containing polyol, isophorone diisocyanate and catalyzer are mixed, and reaction obtains polyurethane prepolymer;
    (2)将步骤(1)得到的聚氨酯预聚物、改性氧化石墨烯和扩链剂混合,反应得到聚氨酯弹性体;(2) mixing the polyurethane prepolymer obtained in step (1), modified graphene oxide and chain extender, and reacting to obtain a polyurethane elastomer;
    (3)将步骤(2)得到的聚氨酯弹性体和改性多孔二氧化硅混合搅拌,挤出成型,得到所述电子产品用高透明TPU薄膜。(3) mixing and stirring the polyurethane elastomer obtained in step (2) and the modified porous silica, and extrusion molding to obtain the high-transparency TPU film for electronic products.
  8. 根据权利要求7所述的制备方法,其特征在于,步骤(1)所述反应的温度为80-120℃,所述反应的时间为2-4h;The preparation method according to claim 7, wherein the temperature of the reaction in step (1) is 80-120°C, and the time of the reaction is 2-4h;
    优选地,步骤(2)所述反应的温度为70-80℃,所述反应的时间为2-4h。Preferably, the temperature of the reaction in step (2) is 70-80° C., and the reaction time is 2-4 h.
  9. 根据权利要求7或8所述的制备方法,其特征在于,步骤(3)所述混合搅拌的温度为50-60℃,所述混合搅拌的时间为20-30min;The preparation method according to claim 7 or 8, wherein the temperature of the mixing and stirring in step (3) is 50-60° C., and the time of the mixing and stirring is 20-30 min;
    优选地,步骤(3)所述挤出成型采用双螺杆挤出机进行,所述双螺杆挤出机的混合段温度为160-170℃,所述双螺杆挤出机的挤出段温度为170-180℃,所述双螺杆挤出机的机头温度为160-170℃。Preferably, the extrusion molding in step (3) is carried out with a twin-screw extruder, the temperature of the mixing section of the twin-screw extruder is 160-170° C., and the temperature of the extrusion section of the twin-screw extruder is 170-180°C, and the temperature of the die head of the twin-screw extruder is 160-170°C.
  10. 根据权利要求7-9中任一项所述的制备方法,其特征在于,所述电子产品用高透明TPU薄膜的制备方法包括以下步骤:The preparation method according to any one of claims 7-9, wherein the preparation method of the high-transparency TPU film for electronic products comprises the following steps:
    (1)将聚酯多元醇、聚乙二醇、含氟多元醇、异佛尔酮二异氰酸酯和催化剂混合,在80-120℃下反应2-4h,得到聚氨酯预聚物;(1) mixing polyester polyol, polyethylene glycol, fluorine-containing polyol, isophorone diisocyanate and a catalyst, and reacting at 80-120° C. for 2-4 hours to obtain a polyurethane prepolymer;
    (2)将步骤(1)得到的聚氨酯预聚物、改性氧化石墨烯和扩链剂混合,在70-80℃下反应2-4h,得到聚氨酯弹性体;(2) mixing the polyurethane prepolymer obtained in step (1), modified graphene oxide and chain extender, and reacting at 70-80° C. for 2-4 hours to obtain a polyurethane elastomer;
    (3)将步骤(2)得到的聚氨酯弹性体和改性多孔二氧化硅在50-60℃混合搅拌20-30min,采用双螺杆挤出机挤出,所述双螺杆挤出机的混合段温度为160-170℃,所述双螺杆挤出机的挤出段温度为170-180℃,所述双螺杆挤出机的机头温度为160-170℃,再利用单螺杆挤出流延成膜或吹塑成膜,得到所述电 子产品用高透明TPU薄膜。(3) The polyurethane elastomer obtained in step (2) and the modified porous silica are mixed and stirred at 50-60° C. for 20-30 minutes, and extruded by a twin-screw extruder. The mixing section of the twin-screw extruder The temperature is 160-170°C, the temperature of the extrusion section of the twin-screw extruder is 170-180°C, the temperature of the head of the twin-screw extruder is 160-170°C, and then the single-screw extruder is used for extrusion casting. Film-forming or blow-molding film-forming to obtain the high-transparency TPU film for electronic products.
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115181820A (en) * 2022-06-24 2022-10-14 福建裕隆纺纱有限公司 Waterproof wear-resistant artificial leather and manufacturing process thereof
CN115216044A (en) * 2022-08-25 2022-10-21 杭州和顺科技股份有限公司 High-light-transmission high-breakdown-voltage backboard and preparation method thereof
CN116239884A (en) * 2023-02-22 2023-06-09 高梵(浙江)信息技术有限公司 Waterproof breathable film for fabric and preparation method thereof
CN116281989A (en) * 2023-04-12 2023-06-23 江西省科学院应用化学研究所 Borneol camphor active molecule modified graphene film and preparation method thereof
CN117430786A (en) * 2023-12-22 2024-01-23 山东一诺威聚氨酯股份有限公司 High-strength TPU material for charging pile cable and preparation method thereof

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113334880A (en) * 2021-05-31 2021-09-03 东莞市雄林新材料科技股份有限公司 High-strength polyurethane composite cloth for inflation and preparation method thereof

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001114859A (en) * 1999-10-08 2001-04-24 Bayer Corp Flexible, transparent and workable thermoplastic polyurethane
CN103508461A (en) * 2012-06-29 2014-01-15 中国科学院大连化学物理研究所 Method for preparing hollow silicon dioxide nanometer particles
CN105085861A (en) * 2015-09-07 2015-11-25 东莞市雄林新材料科技股份有限公司 TPU film with high strength and high thermal stability and preparation method thereof
CN107141441A (en) * 2017-06-02 2017-09-08 东莞市吉鑫高分子科技有限公司 A kind of low-refraction high transparency TPUE and preparation method thereof
CN107987239A (en) * 2017-12-13 2018-05-04 郑小华 A kind of waterproof and breathable TPU film and preparation method thereof
WO2019145391A1 (en) * 2018-01-25 2019-08-01 Nanogate Se Photochromic optically transparent electrically conductive film laminate
CN111138631A (en) * 2020-01-21 2020-05-12 福州大学 Preparation method of high-strength high-barrier TPU composite material
CN111205433A (en) * 2020-01-07 2020-05-29 苏州中来光伏新材股份有限公司 Preparation method of organic fluorine modified polyurethane elastomer resin, coating and back plate
CN111548472A (en) * 2020-06-24 2020-08-18 山东科力美实业有限公司 High-weather-resistance ultra-transparent thermoplastic polyurethane elastomer and preparation method thereof
CN112375201A (en) * 2020-11-30 2021-02-19 山东一诺威聚氨酯股份有限公司 High-strength low-hardness antibacterial deodorant TPU and preparation method thereof

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103788324A (en) * 2005-09-30 2014-05-14 路博润高级材料公司 Thermoplastic polyurethane containing structural units of polyester and polyether diols
KR101247227B1 (en) * 2005-12-08 2013-03-25 루브리졸 어드밴스드 머티어리얼스, 인코포레이티드 Thermoplastic Polyurethane Elastomer with Enhanced Transparency
CN104193957B (en) * 2014-09-17 2017-07-18 曹炜 A kind of transparent TPU film and preparation method thereof
CN107118327A (en) * 2017-06-16 2017-09-01 陕西科技大学 A kind of fluorine alcohol end-sealed type super branched polyurethane of color inhibition and preparation method thereof
CN109137549A (en) * 2018-03-15 2019-01-04 浙江德美博士达高分子材料有限公司 The preparation method of three proofings synthetic leather
CN109354666B (en) * 2018-09-11 2020-12-11 东莞市吉鑫高分子科技有限公司 Low-temperature-resistant thermoplastic polyurethane elastomer and preparation method thereof
CN109437921B (en) * 2018-12-27 2021-08-24 沈阳金瓷科技开发有限责任公司 Method for preparing silicon nitride ceramic powder based on surface modification and low-temperature synthesis
CN110894278B (en) * 2019-11-25 2021-09-28 东莞市吉鑫高分子科技有限公司 High-transparency thermoplastic polyurethane elastomer for film blowing and preparation method thereof

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001114859A (en) * 1999-10-08 2001-04-24 Bayer Corp Flexible, transparent and workable thermoplastic polyurethane
CN103508461A (en) * 2012-06-29 2014-01-15 中国科学院大连化学物理研究所 Method for preparing hollow silicon dioxide nanometer particles
CN105085861A (en) * 2015-09-07 2015-11-25 东莞市雄林新材料科技股份有限公司 TPU film with high strength and high thermal stability and preparation method thereof
CN107141441A (en) * 2017-06-02 2017-09-08 东莞市吉鑫高分子科技有限公司 A kind of low-refraction high transparency TPUE and preparation method thereof
CN107987239A (en) * 2017-12-13 2018-05-04 郑小华 A kind of waterproof and breathable TPU film and preparation method thereof
WO2019145391A1 (en) * 2018-01-25 2019-08-01 Nanogate Se Photochromic optically transparent electrically conductive film laminate
CN111205433A (en) * 2020-01-07 2020-05-29 苏州中来光伏新材股份有限公司 Preparation method of organic fluorine modified polyurethane elastomer resin, coating and back plate
CN111138631A (en) * 2020-01-21 2020-05-12 福州大学 Preparation method of high-strength high-barrier TPU composite material
CN111548472A (en) * 2020-06-24 2020-08-18 山东科力美实业有限公司 High-weather-resistance ultra-transparent thermoplastic polyurethane elastomer and preparation method thereof
CN112375201A (en) * 2020-11-30 2021-02-19 山东一诺威聚氨酯股份有限公司 High-strength low-hardness antibacterial deodorant TPU and preparation method thereof

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115181820A (en) * 2022-06-24 2022-10-14 福建裕隆纺纱有限公司 Waterproof wear-resistant artificial leather and manufacturing process thereof
CN115181820B (en) * 2022-06-24 2024-02-09 福建裕隆纺纱有限公司 Waterproof wear-resistant artificial leather and manufacturing process thereof
CN115216044A (en) * 2022-08-25 2022-10-21 杭州和顺科技股份有限公司 High-light-transmission high-breakdown-voltage backboard and preparation method thereof
CN116239884A (en) * 2023-02-22 2023-06-09 高梵(浙江)信息技术有限公司 Waterproof breathable film for fabric and preparation method thereof
CN116239884B (en) * 2023-02-22 2024-04-09 高梵(浙江)信息技术有限公司 Waterproof breathable film for fabric and preparation method thereof
CN116281989A (en) * 2023-04-12 2023-06-23 江西省科学院应用化学研究所 Borneol camphor active molecule modified graphene film and preparation method thereof
CN116281989B (en) * 2023-04-12 2024-02-13 江西省科学院应用化学研究所 Borneol camphor active molecule modified graphene film and preparation method thereof
CN117430786A (en) * 2023-12-22 2024-01-23 山东一诺威聚氨酯股份有限公司 High-strength TPU material for charging pile cable and preparation method thereof
CN117430786B (en) * 2023-12-22 2024-04-23 山东一诺威聚氨酯股份有限公司 High-strength TPU material for charging pile cable and preparation method thereof

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