WO2022041614A1 - Microporous repairable tpu thin film material and preparation method therefor - Google Patents

Microporous repairable tpu thin film material and preparation method therefor Download PDF

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Publication number
WO2022041614A1
WO2022041614A1 PCT/CN2020/140455 CN2020140455W WO2022041614A1 WO 2022041614 A1 WO2022041614 A1 WO 2022041614A1 CN 2020140455 W CN2020140455 W CN 2020140455W WO 2022041614 A1 WO2022041614 A1 WO 2022041614A1
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film material
parts
repairable
microporous
tpu film
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PCT/CN2020/140455
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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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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
    • C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4833—Polyethers containing oxyethylene units
    • C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2451/02—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to polysaccharides

Definitions

  • the invention belongs to the technical field of polymer materials, in particular to a TPU film material and a preparation method thereof, in particular to a microporous repairable TPU film material and a preparation method thereof.
  • polyurethane As a general-purpose industrial plastic, polyurethane has the characteristics of wear resistance, good elasticity, not easy to break, and resistance to bending. Especially when polyurethane uses water as a solvent, it also has the advantages of safety, reliability, no pollution, and easy handling. And most water-based polyurethanes have a microsphere-like structure on the microscopic level, which can be used as the cross-linking point of the composite material, thus playing the role of fixing and strengthening, and giving the composite material some special properties. However, when the polyurethane material is subjected to external mechanical action, it is easy to cause damage to the surface or interior of the material, causing cracks or holes in the material, which has a serious impact on the mechanical properties and service life of the material. Efficiency is essential.
  • CN108059823A provides a TPU material with thermal self-repair and a preparation method thereof.
  • the raw material of the TPU material includes the following components in parts by mass: 50-60 parts of diisocyanate, 35-50 parts of polyol, 0.002-0.1 part of graphene, 0.002-0.2 part of carbon nanotube, 2-acrylamido-2 -5-10 parts of methyl-1-propane sulfonic acid, 15-30 parts of styrene-acrylonitrile copolymer, 2-8 parts of chain extender, 0.1-10 parts of catalyst.
  • the TPU material optimizes the self-healing ability of the material by introducing carbon nanotubes. However, it can only improve the thermal self-healing ability by promoting edge softening, and the repairing ability of the holes in the TPU material is poor.
  • CN110551351A provides a polyurethane biomimetic self-healing composite material and a preparation method thereof.
  • the polyurethane biomimetic self-healing composite material is made from the following raw materials in parts by mass: 40-70 parts of polyvinyl alcohol, 5-10 parts of polyphenol structural compounds, 1-5 parts of ferric compounds, and 10-5 parts of polyurethane emulsion. 20 servings.
  • the polyurethane biomimetic self-healing composite material has good self-healing ability and mechanical properties, and finally endows the composite material with a certain self-healing function through the microstructure of multiple hydrogen bonds and metal coordination bonds between the mussel-like byssula structures. However, the repairing ability of holes in TPU materials is also poor.
  • the purpose of the present invention is to provide a TPU film material, especially a microporous repairable TPU film material.
  • the TPU film material has excellent mechanical properties and self-healing function, especially for the hole repairing performance made on the film.
  • the present invention provides a microporous repairable TPU film material, and the preparation raw materials of the microporous repairable TPU film material include the following components in parts by weight:
  • the TPU film material improves the mobility of segments by introducing disulfide bonds into the main chain of the polyurethane, and at the same time uses the boric acid ester bonds constructed by boric acid to form a reversible cross-linked network, so that a cross-linked network structure is formed inside the polyurethane.
  • a repairable TPU film material with high strength, high toughness and high repair efficiency was prepared.
  • the sulfide chain extender provides disulfide bonds, and at a certain temperature, the disulfide bonds on the main chain undergo dynamic disulfide exchange reaction, which can promote the mutual diffusion and entanglement between segments;
  • Boric acid is used as a crosslinking agent , on the one hand, it can improve the mechanical strength of the material, so that the sample can remain stable in the normal use environment;
  • the structure is disentangled, and the molecular chains at both ends of the fracture surface can move, diffuse and entangle freely, and gradually complete the fracture repair.
  • the present invention also introduces furan groups, a large number of urea groups and maleimide rings by adding furfurylamine graft-modified alkali lignin and maleimide to graft cellulose nanocrystals.
  • the combination has a synergistic effect, which can not only further improve the self-healing ability of the polyurethane but also improve the mechanical properties of the polyurethane.
  • furfurylamine graft-modified alkali lignin is prepared by grafting lignin with furfurylamine and diisocyanate after alkali and aldehyde hydroxylation; while maleimide-grafted cellulose nanocrystals are obtained. It is prepared by grafting cellulose nanocrystals and maleimide acid in water.
  • the content of the polyester polyol is 45-55 parts, such as 45 parts, 46 parts, 47 parts, 48 parts, 49 parts, 50 parts, 51 parts, 52 parts, 53 parts, 54 parts , 55 copies, etc.
  • the content of the polyether polyol is 7-15 parts, such as 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, etc.
  • the content of the diisocyanate is 25-35 parts, such as 25 parts, 26 parts, 27 parts, 28 parts, 29 parts, 30 parts, 31 parts, 32 parts, 33 parts, 34 parts, 35 parts copies etc.
  • the content of the thioether chain extender is 1-10 parts, for example, it can be 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts copies etc.
  • the content of the boric acid is 0.5-2 parts, such as 0.5 part, 0.6 part, 0.7 part, 0.8 part, 0.9 part, 1 part, 1.2 part, 1.4 part, 1.6 part, 1.8 part, 2 part Wait.
  • the content of the catalyst is 0.05-0.1 part, such as 0.05 part, 0.06 part, 0.07 part, 0.08 part, 0.09 part, 0.1 part, etc.
  • the content of the furfurylamine graft-modified alkali lignin is 1-5 parts, for example, it can be 1 part, 1.2 parts, 1.4 parts, 1.6 parts, 1.8 parts, 2 parts, 2.5 parts, 2.8 parts , 3 copies, 3.4 copies, 3.7 copies, 4 copies, 4.5 copies, 5 copies, etc.
  • the content of the maleimide-grafted cellulose nanocrystals is 1-5 parts, for example, it can be 1 part, 1.2 parts, 1.4 parts, 1.6 parts, 1.8 parts, 2 parts, 2.5 parts, 2.8 parts servings, 3 servings, 3.4 servings, 3.7 servings, 4 servings, 4.5 servings, 5 servings, etc.
  • the weight average molecular weight of the polyester polyol is 1000-3000, such as 1000, 1200, 1500/1800, 2000, 2200, 2500, 2800, 3000 and the like.
  • the polyester polyol is selected from polybutylene succinate, polybutylene adipate, polyhexamethylene adipate or polybutylene glycol adipate any one or a combination of at least two.
  • the weight average molecular weight of the polyether polyol is 1000-3000, such as 1000, 1200, 1500/1800, 2000, 2200, 2500, 2800, 3000, and the like.
  • the polyether polyol is selected from the group consisting of polyoxypropylene diol, polyoxyethylene diol, polyoxypropylene polyether triol, oxypropylene-ethylene oxide copolymer triol, polytetrahydrofuran diol or tetrahydrofuran-ethylene oxide copolymer Any one or a combination of at least two of the diols, preferably polytetrahydrofuran diol and/or tetrahydrofuran-ethylene oxide copolymer diol.
  • the diisocyanate is selected from any one or a combination of at least two of isophorone diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate or hexamethylene diisocyanate, preferably hexamethylene diisocyanate base diisocyanate.
  • the thioether chain extender is selected from 4,4'-diaminodiphenyldisulfide, 2,2'-diaminodiphenyldisulfide, 3,3'-dihydroxydiphenyldisulfide , any one or a combination of at least two of 4,4'-dihydroxydiphenyl disulfide or bis(2-hydroxyethyl) disulfide.
  • the catalyst is selected from any one or a combination of at least two of dibutyltin dilaurate, stannous octoate, cobalt octoate or N-methylmorpholine.
  • the preparation raw materials of the microporous repairable TPU film material further include 0.1-0.5 parts of lubricant, such as 0.1 part, 0.2 part, 0.3 part, 0.4 part, 0.5 part, etc.
  • the lubricant is selected from any one or a combination of at least two of glycerol monostearate, stearic acid amide, ethylene bis stearic acid amide, E wax or oleic acid amide.
  • the present invention provides a preparation method for obtaining a microporous repairable TPU film material as described in the first aspect, and the preparation method for the microporous repairable TPU film material comprises the following steps:
  • step (2) mixing the polyurethane prepolymer, thioether chain extender and boric acid obtained in step (1), and reacting to obtain polyurethane prepolymer II;
  • step (3) mixing and stirring the polyurethane prepolymer 2 obtained in step (2) and the maleimide-grafted cellulose nanocrystals, and extruding to obtain the microporous repairable TPU film material.
  • the temperature of the reaction in step (1) is 100-120°C, such as 100°C, 102°C, 105°C, 108°C, 110°C, 112°C, 115°C, 118°C, 120°C, etc., so
  • the reaction time is 2-4h, for example, it can be 2h, 2.5h, 3h, 3.5h, 4h and the like.
  • the temperature of the reaction in step (2) is 80-90°C, such as 80°C, 82°C, 84°C, 86°C, 88°C, 90°C, etc.
  • the reaction time is 1-3h, For example, it can be 1h, 1.5h, 2h, 2.5h, 3h and so on.
  • the temperature of the mixing and stirring in step (3) is 60-70°C, such as 60°C, 62°C, 64°C, 66°C, 68°C, 70°C, etc.
  • the mixing and stirring time is 30- 60min, for example, can be 30min, 35min, 40min, 45min, 50min, 55min, 60min and the like.
  • the extrusion molding in step (3) is performed by a twin-screw extruder, and the temperature of the mixing section of the twin-screw extruder is 130-150°C, for example, 130°C, 135°C, 140°C, 145°C , 150°C, etc., the extrusion temperature is 180-190°C, for example, it can be 180°C, 182°C, 184°C, 186°C, 188°C, 190°C, etc., and the screw speed is 300-500r/min, for example, it can be 300r /min, 350r/min, 400r/min, 450r/min, 500r/min, etc.
  • the preparation method of the microporous repairable TPU film material comprises the following steps:
  • step (2) mixing the polyurethane prepolymer obtained in step (1), the thioether chain extender and boric acid, and reacting at 80-90° C. for 1-3 hours to obtain polyurethane prepolymer II;
  • step (3) mixing and stirring the polyurethane prepolymer II, maleimide-grafted cellulose nanocrystals and lubricant obtained in step (2) at 60-70 ° C for 30-60 min, and extruding with a twin-screw extruder,
  • the temperature of the mixing section of the twin-screw extruder is 130-150°C
  • the temperature of the extrusion section is 180-190°C
  • the screw speed is 300-500r/min
  • the single-screw extruder is used to extrude and cast a film or blow a film. , to obtain the microporous repairable TPU film material.
  • the present invention has the following beneficial effects:
  • the TPU film material of the present invention is composed of an appropriate proportion of polyester polyol, polyether polyol, diisocyanate, thioether chain extender, boric acid, catalyst, furfurylamine graft-modified alkali lignin and maleic acid
  • the imide-grafted cellulose nanocrystals are prepared.
  • it takes into account the characteristics of self-healing performance and mild repair conditions, especially for the excellent hole repair performance of the film.
  • the tensile strength of the TPU film material of the present invention is above 40 MPa, and the elongation at break is as high as 600% or more; and the holes with a diameter of less than 2 cm are extremely repairable and can be repaired at 40-60 ° C. After the high temperature treatment, the holes on the TPU film material can be automatically healed, and the self-healing efficiency is as high as 98%. above.
  • furfurylamine graft-modified alkali lignin and maleimide-grafted cellulose nanocrystals in the following examples are prepared from Preparation Example 1 and Preparation Example 2, and other components are commercially available products.
  • This preparation example provides a furfurylamine graft-modified alkali lignin, and the preparation method of the furfurylamine graft-modified alkali lignin comprises the following steps:
  • This preparation example provides a maleimide-grafted cellulose nanocrystal, and the preparation method of the maleimide-grafted cellulose nanocrystal is as follows: 30 parts of 10wt% cellulose nanocrystal water dispersion , 10 parts of 6-maleimide caproic acid and 10 parts of deionized water are mixed evenly, heated to 100° C. to react for 6 hours, filtered, and rotary steamed to obtain the maleimide-grafted cellulose nanocrystals.
  • the present embodiment provides a microporous repairable TPU film material, and the preparation method of the microporous repairable TPU film material includes the following steps:
  • step (2) mixing the polyurethane prepolymer obtained in step (1), 5 parts of 4,4'-diaminodiphenyl disulfide and 1 part of boric acid, and reacting at 85° C. for 2 hours to obtain polyurethane prepolymer II;
  • step (3) Two parts of the polyurethane prepolymer obtained in step (2), 2 parts of maleimide-grafted cellulose nanocrystals and 0.2 part of glycerol monostearate were mixed and stirred at 65° C. for 40 minutes, and a twin screw was used.
  • the temperature of the mixing section of the twin-screw extruder is 140 ° C
  • the temperature of the extrusion section is 185 ° C
  • the screw speed is 400 r/min
  • the single-screw extrusion is used to cast a film to obtain the micro Hole repairable TPU film material.
  • the present embodiment provides a microporous repairable TPU film material, and the preparation method of the microporous repairable TPU film material includes the following steps:
  • step (2) mixing the polyurethane prepolymer obtained in step (1), 4 parts of 2,2′-diaminodiphenyldisulfide and 1.5 parts of boric acid, and reacting at 80° C. for 3 hours to obtain polyurethane prepolymer II;
  • the present embodiment provides a microporous repairable TPU film material, and the preparation method of the microporous repairable TPU film material includes the following steps:
  • step (2) mixing the polyurethane prepolymer obtained in step (1), 8 parts of 2,2'-diaminodiphenyl disulfide and 1.2 parts of boric acid, and reacting at 90° C. for 1 h to obtain polyurethane prepolymer II;
  • step (3) The polyurethane prepolymer 2 obtained in step (2), 1.5 parts of maleimide-grafted cellulose nanocrystals and 0.2 parts of glycerol monostearate were mixed and stirred at 70° C. for 30 minutes, using twin screw Extruder extruder, the temperature of the mixing section of the twin-screw extruder is 140 ° C, the temperature of the extrusion section is 190 ° C, the screw speed is 500 r/min, and then the single-screw extrusion is used to cast a film to obtain the micro Hole repairable TPU film material.
  • the present embodiment provides a microporous repairable TPU film material, and the preparation method of the microporous repairable TPU film material includes the following steps:
  • step (2) mixing the polyurethane prepolymer obtained in step (1), 5 parts of 4,4'-diaminodiphenyl disulfide and 1 part of boric acid, and reacting at 85° C. for 2 hours to obtain polyurethane prepolymer II;
  • step (3) 2 parts of the polyurethane prepolymer obtained in step (2), 3 parts of furfurylamine graft-modified alkali lignin and 0.2 part of glycerol monostearate were mixed and stirred at 65°C for 40min, and the twin-screw extrusion was adopted.
  • the temperature of the mixing section of the twin-screw extruder is 140 ° C
  • the temperature of the extrusion section is 185 ° C
  • the screw speed is 400 r/min
  • the single-screw extrusion is used to cast a film to obtain the micropores. Repairable TPU film material.
  • the present embodiment provides a microporous repairable TPU film material, and the preparation method of the microporous repairable TPU film material includes the following steps:
  • step (2) mixing the polyurethane prepolymer obtained in step (1), 5 parts of 4,4'-diaminodiphenyl disulfide and 1 part of boric acid, and reacting at 85° C. for 2 hours to obtain polyurethane prepolymer II;
  • step (3) The polyurethane prepolymer obtained in step (2) and 0.2 part of glycerol monostearate were mixed and stirred at 65° C. for 40 minutes, and extruded by a twin-screw extruder.
  • the mixing section of the twin-screw extruder The temperature is 140° C., the temperature of the extrusion section is 185° C., the screw speed is 400 r/min, and the single-screw extrusion casting film is used to obtain the microporous repairable TPU film material.
  • This embodiment provides a microporous repairable TPU film material.
  • the only difference from Embodiment 1 is that the polytetrahydrofuran diol (weight average molecular weight is 2000) is replaced with polyoxypropylene glycol (weight average molecular weight is 2000) ), the content of other components and the preparation method are the same as in Example 1.
  • This embodiment provides a microporous repairable TPU film material.
  • the only difference from Embodiment 1 is that hexamethylene diisocyanate is replaced with isophorone diisocyanate, and the contents and preparation methods of other components are the same as those in Embodiment 1. .
  • This embodiment provides a microporous repairable TPU film material.
  • the only difference from Example 1 is that no lubricant is added to the preparation raw material of the microporous repairable TPU film material, and the contents of other components and the preparation method are the same as the implementation. example 1.
  • This comparative example provides a TPU film material.
  • the only difference from Example 1 is that in step (2), 4,4'-diaminodiphenyl disulfide is no longer added, and the content of boric acid is increased to 6 parts.
  • the content and preparation method are the same as those in Example 1.
  • This comparative example provides a TPU film material.
  • the only difference from Example 1 is that in step (2), no boric acid is added, and the content of 4,4'-diaminodiphenyldisulfide is increased to 6 parts.
  • the content and preparation method are the same as those in Example 1.
  • This comparative example provides a TPU film material, which differs from Example 1 only in that 4,4'-diaminodiphenyldisulfide is replaced with ethylene glycol, and the contents and preparation methods of other components are the same as those of Example 1.
  • This comparative example provides a TPU film material, which differs from Example 1 only in that the content of 4,4'-diaminodiphenyldisulfide in step (2) is reduced to 3 parts, the content of boric acid is increased to 6 parts, and other Component content and preparation method are the same as in Example 1.
  • This comparative example provides a TPU film material, the only difference from Example 1 is that in step (1), furfurylamine graft-modified alkali lignin is no longer added, and in step (3), maleimide is grafted
  • the content of cellulose nanocrystals was increased to 5 parts, and the content of other components and the preparation method were the same as those of Example 1.
  • This comparative example provides a TPU film material, which differs from Example 1 only in that in step (3), maleimide is not added to graft cellulose nanocrystals, and in step (1), furfurylamine is grafted and modified
  • the content of alkali lignin was increased to 5 parts, and the content of other components and the preparation method were the same as those of Example 1.
  • This comparative example provides a TPU film material, the only difference from Example 1 is that polybutylene succinate is no longer added in step (1), and the content of polytetrahydrofurandiol is increased to 60 parts, and other components
  • the content and preparation method are the same as those in Example 1.
  • This comparative example provides a TPU film material, the only difference from Example 1 is that polytetrahydrofuran diol is no longer added in step (1), and the content of polybutylene succinate is increased to 60 parts, and other components
  • the content and preparation method are the same as those in Example 1.
  • the tensile strength of the TPU film material of the present invention is above 40MPa, and the elongation at break is as high as 600% or more; After the heating treatment of 40-60°C, the holes on the TPU film material can be healed automatically, and the self-healing efficiency is as high as 98%. The tensile strength of the healed TPU film material can still be maintained above 40MPa, and the elongation at break can still be maintained above 600%.
  • the present invention takes into account the characteristics of self-healing performance and mild repair conditions on the basis of ensuring that the TPU film material has good mechanical properties, especially for the excellent hole repairing performance made by the film, and solves the mechanical properties and self-healing properties of the previous self-healing materials. Fix performance incompatibility issues.
  • Example 1 and Examples 4 and 5 From the comparison of Example 1 and Examples 4 and 5, it can be seen that the order of addition of furfurylamine graft-modified alkali lignin and maleimide grafted cellulose nanocrystals has a certain effect on the structure of the TPU film material prepared by the present invention. Influence, the TPU film material prepared according to the preparation method of the present invention has stronger mechanical properties and better repairing ability. It can be seen from the comparison between Example 1 and Examples 6 and 7 that the mechanical properties and self-healing properties of the prepared TPU film material are improved more obviously by using the preferred polyether polyol and diisocyanate of the present invention.
  • Example 1 From the comparison between Example 1 and Comparative Examples 1-3, it can be seen that the present invention improves the mobility of segments by introducing disulfide bonds into the main chain of the polyurethane, and at the same time uses the boric acid ester bonds constructed by boronic acid to form a reversible cross-linked network, so that the polyurethane A cross-linked network structure is formed inside, and a repairable TPU film material with high repair efficiency is obtained.
  • the TPU film material prepared without either sulfide chain extender or boric acid has no repair ability, and the pores cannot be healed.
  • Example 1 Comparative Example 4
  • the mechanical properties and self-healing properties of the prepared TPU film material can be further improved.
  • Example 1 From the comparison between Example 1 and Comparative Examples 5 and 6, it can be seen that the alkali lignin grafted with furfurylamine and the maleimide grafted cellulose nanocrystals cooperate with each other and have a synergistic effect, which can not only further improve the The self-healing ability of polyurethane can also improve the mechanical properties of polyurethane.
  • the polyol of the present invention selects polyester polyol and polyether polyol to cooperate with each other, which can better introduce disulfide bonds in the main chain of polyurethane, and construct The boronate bond formed a reversible cross-linked network, and the mechanical properties and self-healing properties of the prepared TPU film material were improved more obviously.
  • the present invention describes the microporous repairable TPU film material and its preparation method by the above-mentioned examples, but the present invention is not limited to the above-mentioned examples, that is to say, it does not mean that the present invention can only be implemented by relying on the above-mentioned examples. .
  • Those skilled in the art should understand that any improvement to 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

A microporous repairable TPU thin film material and a preparation method therefor. The raw materials for preparing the microporous repairable TPU thin film material comprise the following components in parts by weight: 45-55 parts of polyester polyol, 7-15 parts of polyether polyol, 25-35 parts of diisocyanate, 1-10 parts of a thioether chain extender, 0.5-2 parts of boric acid, 0.05-0.1 parts of a catalyst, 1-5 parts of alkali lignin modified by grafted furfurylamine, and 1-5 parts of maleimide-grafted cellulose nanocrystals. The described TPU thin film material has excellent mechanical performance and a repairing function, in particular having a significant effect in repairing holes made on a thin film.

Description

一种微孔可修复TPU薄膜材料及其制备方法A kind of microporous repairable TPU film material and preparation method thereof
本公开基于申请号为202010870507.8，申请日为2020年08月26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 202010870507.8 and the filing date on August 26, 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薄膜材料及其制备方法，尤其涉及一种微孔可修复TPU薄膜材料及其制备方法。The invention belongs to the technical field of polymer materials, in particular to a TPU film material and a preparation method thereof, in particular to a microporous repairable TPU film material and a preparation method thereof.
背景技术Background technique
聚氨酯作为一种通用的工业塑料，具有耐磨耗、弹性好、不易断裂、以及耐弯曲等特性，尤其是聚氨酯以水作为溶剂时，还具有安全可靠，无污染，易处理等优势。并且大多数水性聚氨酯在微观上呈现出微球型的结构，可以作为复合材料的交联点，从而起到固定与增强的作用，并赋予复合材料一些特殊性能。但当聚氨酯材料在受到外部机械作用时，容易对材料表面或内部造成损伤，使材料产生裂纹或孔洞，对材料的力学性能及使用寿命造成严重影响，因此修复对延长材料的使用寿命、提高使用效率不可或缺。As a general-purpose industrial plastic, polyurethane has the characteristics of wear resistance, good elasticity, not easy to break, and resistance to bending. Especially when polyurethane uses water as a solvent, it also has the advantages of safety, reliability, no pollution, and easy handling. And most water-based polyurethanes have a microsphere-like structure on the microscopic level, which can be used as the cross-linking point of the composite material, thus playing the role of fixing and strengthening, and giving the composite material some special properties. However, when the polyurethane material is subjected to external mechanical action, it is easy to cause damage to the surface or interior of the material, causing cracks or holes in the material, which has a serious impact on the mechanical properties and service life of the material. Efficiency is essential.
CN108059823A提供了一种具有热自修复的TPU材料及其制备方法。所述TPU材料的原料包括如下质量份数的成分：二异氰酸酯50-60份、多元醇35-50份、石墨烯0.002-0.1份、碳纳米管0.002-0.2份、2-丙烯酰胺基-2-甲基-1-丙烷磺酸5-10份、苯乙烯-丙烯腈共聚物15-30份、扩链剂2-8份、催化剂0.1-10份。该TPU材料通过引入碳纳米管，优化了材料自修复能力，然而其仅能通过促进边缘软化，从而提高热自修复能力，对于TPU材料出现的孔洞修复能力较差。CN108059823A provides a TPU material with thermal self-repair and a preparation method thereof. The raw material of the TPU material includes the following components in parts by mass: 50-60 parts of diisocyanate, 35-50 parts of polyol, 0.002-0.1 part of graphene, 0.002-0.2 part of carbon nanotube, 2-acrylamido-2 -5-10 parts of methyl-1-propane sulfonic acid, 15-30 parts of styrene-acrylonitrile copolymer, 2-8 parts of chain extender, 0.1-10 parts of catalyst. The TPU material optimizes the self-healing ability of the material by introducing carbon nanotubes. However, it can only improve the thermal self-healing ability by promoting edge softening, and the repairing ability of the holes in the TPU material is poor.
CN110551351A提供了一种聚氨酯仿生自修复复合材料及其制备方法。所 述的聚氨酯仿生自修复复合材料，由以下质量份数的原料制成：聚乙烯醇40-70份，多酚结构化合物5-10份，三价铁化合物1-5份，聚氨酯乳液10-20份。该聚氨酯仿生自修复复合材料，具有良好的自修复能力和机械性能，通过仿贻贝足丝结构之间的多重氢键与金属配位键的微观结构，最终赋予复合材料一定的自修复功能，但同样对于TPU材料出现的孔洞修复能力较差。CN110551351A provides a polyurethane biomimetic self-healing composite material and a preparation method thereof. The polyurethane biomimetic self-healing composite material is made from the following raw materials in parts by mass: 40-70 parts of polyvinyl alcohol, 5-10 parts of polyphenol structural compounds, 1-5 parts of ferric compounds, and 10-5 parts of polyurethane emulsion. 20 servings. The polyurethane biomimetic self-healing composite material has good self-healing ability and mechanical properties, and finally endows the composite material with a certain self-healing function through the microstructure of multiple hydrogen bonds and metal coordination bonds between the mussel-like byssula structures. However, the repairing ability of holes in TPU materials is also poor.
因此，开发一种微孔可修复TPU薄膜材料是本领域研究的重点。Therefore, developing a microporous repairable TPU film material is the focus of research in this field.
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TPU薄膜材料，特别是提供一种微孔可修复TPU薄膜材料。所述TPU薄膜材料优良的机械性能和自修复功能，尤其对于薄膜上做出的孔洞修复性能优异。In view of the deficiencies of the prior art, the purpose of the present invention is to provide a TPU film material, especially a microporous repairable TPU film material. The TPU film material has excellent mechanical properties and self-healing function, especially for the hole repairing performance made on the film.
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，本发明提供一种微孔可修复TPU薄膜材料，所述微孔可修复TPU薄膜材料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 microporous repairable TPU film material, and the preparation raw materials of the microporous repairable TPU film material include the following components in parts by weight:
Figure PCTCN2020140455-appb-000001
Figure PCTCN2020140455-appb-000001
在本发明中，所述TPU薄膜材料通过在聚氨酯的主链中引入二硫键提高链段运动能力，同时利用硼酸构建的硼酸酯键形成可逆交联网络，使聚氨酯内部 形成交联网络结构，制备了一种兼具高强度、高韧性及高修复效率的可修复TPU薄膜材料。其中，硫醚扩链剂提供二硫键，在一定温度下，主链上的二硫键发生动态二硫交换反应，可以促进链段之间的相互扩散和缠结；采用硼酸作为交联剂，一方面可以提高材料的力学强度，使试样在常规使用环境中能够保持稳定，另一方面，硼酸酯键能够进行可逆水解反应，TPU薄膜材料出现孔洞后，试样断面处的交联结构被解开，断裂面两端的分子链可以自由运动、扩散和缠结，逐渐完成断面修复。In the present invention, the TPU film material improves the mobility of segments by introducing disulfide bonds into the main chain of the polyurethane, and at the same time uses the boric acid ester bonds constructed by boric acid to form a reversible cross-linked network, so that a cross-linked network structure is formed inside the polyurethane. , a repairable TPU film material with high strength, high toughness and high repair efficiency was prepared. Among them, the sulfide chain extender provides disulfide bonds, and at a certain temperature, the disulfide bonds on the main chain undergo dynamic disulfide exchange reaction, which can promote the mutual diffusion and entanglement between segments; Boric acid is used as a crosslinking agent , on the one hand, it can improve the mechanical strength of the material, so that the sample can remain stable in the normal use environment; The structure is disentangled, and the molecular chains at both ends of the fracture surface can move, diffuse and entangle freely, and gradually complete the fracture repair.
同时，本发明还通过添加糠胺接枝改性的碱木质素和马来酰亚胺接枝纤维素纳米晶，从而引入呋喃基团、大量脲基及马来酰亚胺环，二者相互配合具有协同增效的作用，不仅可以进一步提高聚氨酯的自修复的能力还可以改善聚氨酯的机械性能。其中，糠胺接枝改性的碱木质素是由木质素经碱和醛羟基化后，再与糠胺和二异氰酸酯进行接枝制备得到的；而马来酰亚胺接枝纤维素纳米晶是由纤维素纳米晶和马来酰亚胺酸在水中接枝制备得到的。At the same time, the present invention also introduces furan groups, a large number of urea groups and maleimide rings by adding furfurylamine graft-modified alkali lignin and maleimide to graft cellulose nanocrystals. The combination has a synergistic effect, which can not only further improve the self-healing ability of the polyurethane but also improve the mechanical properties of the polyurethane. Among them, furfurylamine graft-modified alkali lignin is prepared by grafting lignin with furfurylamine and diisocyanate after alkali and aldehyde hydroxylation; while maleimide-grafted cellulose nanocrystals are obtained. It is prepared by grafting cellulose nanocrystals and maleimide acid in water.
本发明中，所述聚酯多元醇的含量为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 content of the polyester polyol is 45-55 parts, such as 45 parts, 46 parts, 47 parts, 48 parts, 49 parts, 50 parts, 51 parts, 52 parts, 53 parts, 54 parts , 55 copies, etc.
本发明中，所述聚醚多元醇的含量为7-15份，例如可以是7份、8份、9份、10份、11份、12份、13份、14份、15份等。In the present invention, the content of the polyether polyol is 7-15 parts, such as 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, etc.
本发明中，所述二异氰酸酯的含量为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 content of the diisocyanate is 25-35 parts, such as 25 parts, 26 parts, 27 parts, 28 parts, 29 parts, 30 parts, 31 parts, 32 parts, 33 parts, 34 parts, 35 parts copies etc.
本发明中，所述硫醚扩链剂的含量为1-10份，例如可以是1份、2份、3份、4份、5份、6份、7份、8份、9份、10份等。In the present invention, the content of the thioether chain extender is 1-10 parts, for example, it can be 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts copies etc.
本发明中，所述硼酸的含量为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 present invention, the content of the boric acid is 0.5-2 parts, such as 0.5 part, 0.6 part, 0.7 part, 0.8 part, 0.9 part, 1 part, 1.2 part, 1.4 part, 1.6 part, 1.8 part, 2 part Wait.
本发明中，所述催化剂的含量为0.05-0.1份，例如可以是0.05份、0.06份、0.07份、0.08份、0.09份、0.1份等。In the present invention, the content of the catalyst is 0.05-0.1 part, such as 0.05 part, 0.06 part, 0.07 part, 0.08 part, 0.09 part, 0.1 part, etc.
本发明中，所述糠胺接枝改性的碱木质素的含量为1-5份，例如可以是1份、1.2份、1.4份、1.6份、1.8份、2份、2.5份、2.8份、3份、3.4份、3.7份、4份、4.5份、5份等。In the present invention, the content of the furfurylamine graft-modified alkali lignin is 1-5 parts, for example, it can be 1 part, 1.2 parts, 1.4 parts, 1.6 parts, 1.8 parts, 2 parts, 2.5 parts, 2.8 parts , 3 copies, 3.4 copies, 3.7 copies, 4 copies, 4.5 copies, 5 copies, etc.
本发明中，所述马来酰亚胺接枝纤维素纳米晶的含量为1-5份，例如可以是1份、1.2份、1.4份、1.6份、1.8份、2份、2.5份、2.8份、3份、3.4份、3.7份、4份、4.5份、5份等。In the present invention, the content of the maleimide-grafted cellulose nanocrystals is 1-5 parts, for example, it can be 1 part, 1.2 parts, 1.4 parts, 1.6 parts, 1.8 parts, 2 parts, 2.5 parts, 2.8 parts servings, 3 servings, 3.4 servings, 3.7 servings, 4 servings, 4.5 servings, 5 servings, etc.
优选地，所述聚酯多元醇的重均分子量为1000-3000，例如可以是1000、1200、1500/1800、2000、2200、2500、2800、3000等。Preferably, the weight average molecular weight of the polyester polyol is 1000-3000, such as 1000, 1200, 1500/1800, 2000, 2200, 2500, 2800, 3000 and the like.
优选地，所述聚酯多元醇选自聚丁二酸丁二醇酯、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 is selected from polybutylene succinate, polybutylene adipate, polyhexamethylene adipate or polybutylene glycol adipate any one or a combination of at least two.
优选地，所述聚醚多元醇的重均分子量为1000-3000，例如可以是1000、1200、1500/1800、2000、2200、2500、2800、3000等。Preferably, the weight average molecular weight of the polyether polyol is 1000-3000, such as 1000, 1200, 1500/1800, 2000, 2200, 2500, 2800, 3000, and the like.
优选地，所述聚醚多元醇选自聚氧化丙烯二醇、聚氧化乙烯二醇、聚氧化丙烯聚醚三醇、氧化丙烯-氧化乙烯共聚三醇、聚四氢呋喃二醇或四氢呋喃-氧化乙烯共聚物二醇中的任意一种或至少两种的组合，优选为聚四氢呋喃二醇和/或四氢呋喃-氧化乙烯共聚物二醇。Preferably, the polyether polyol is selected from the group consisting of polyoxypropylene diol, polyoxyethylene diol, polyoxypropylene polyether triol, oxypropylene-ethylene oxide copolymer triol, polytetrahydrofuran diol or tetrahydrofuran-ethylene oxide copolymer Any one or a combination of at least two of the diols, preferably polytetrahydrofuran diol and/or tetrahydrofuran-ethylene oxide copolymer diol.
优选地，所述二异氰酸酯选自异佛尔酮二异氰酸酯、甲苯二异氰酸酯、二苯基甲烷二异氰酸酯或六亚甲基二异氰酸酯中的任意一种或至少两种的组合，优选为六亚甲基二异氰酸酯。Preferably, the diisocyanate is selected from any one or a combination of at least two of isophorone diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate or hexamethylene diisocyanate, preferably hexamethylene diisocyanate base diisocyanate.
优选地，所述硫醚扩链剂选自4，4′-二氨基二苯二硫醚、2，2′-二氨基二苯二硫醚、3，3′-二羟基二苯二硫醚、4，4′-二羟基二苯二硫醚或双(2-羟乙基)二硫化物 中的任意一种或至少两种的组合。Preferably, the thioether chain extender is selected from 4,4'-diaminodiphenyldisulfide, 2,2'-diaminodiphenyldisulfide, 3,3'-dihydroxydiphenyldisulfide , any one or a combination of at least two of 4,4'-dihydroxydiphenyl disulfide or bis(2-hydroxyethyl) disulfide.
优选地，所述催化剂选自二月桂酸二丁基锡、辛酸亚锡、辛酸钴或N-甲基吗啉中的任意一种或至少两种的组合。Preferably, the catalyst is selected from any one or a combination of at least two of dibutyltin dilaurate, stannous octoate, cobalt octoate or N-methylmorpholine.
优选地，所述微孔可修复TPU薄膜材料的制备原料中还包括0.1-0.5份润滑剂，例如可以是0.1份、0.2份、0.3份、0.4份、0.5份等。Preferably, the preparation raw materials of the microporous repairable TPU film material further include 0.1-0.5 parts of lubricant, such as 0.1 part, 0.2 part, 0.3 part, 0.4 part, 0.5 part, etc.
优选地，所述润滑剂选自单硬脂酸甘油酯、硬脂酸酰胺、乙撑双硬脂酸酰胺、E蜡或油酸酰胺中的任意一种或至少两种的组合。Preferably, the lubricant is selected from any one or a combination of at least two of glycerol monostearate, stearic acid amide, ethylene bis stearic acid amide, E wax or oleic acid amide.
第二方面，本发明提供一种如第一方面所述得微孔可修复TPU薄膜材料的制备方法，所述微孔可修复TPU薄膜材料的制备方法包括以下步骤：In the second aspect, the present invention provides a preparation method for obtaining a microporous repairable TPU film material as described in the first aspect, and the preparation method for the microporous repairable TPU film material comprises the following steps:
(1)将聚酯多元醇、聚醚多元醇、二异氰酸酯、糠胺接枝改性的碱木质素和催化剂混合，反应得到聚氨酯预聚物一；(1) mixing polyester polyol, polyether polyol, diisocyanate, and furfurylamine graft-modified alkali lignin and catalyst, and reacting to obtain polyurethane prepolymer one;
(2)将步骤(1)得到的聚氨酯预聚物、硫醚扩链剂和硼酸混合，反应得到聚氨酯预聚物二；(2) mixing the polyurethane prepolymer, thioether chain extender and boric acid obtained in step (1), and reacting to obtain polyurethane prepolymer II;
(3)将步骤(2)得到的聚氨酯预聚物二和马来酰亚胺接枝纤维素纳米晶混合搅拌，挤出成型，得到所述微孔可修复TPU薄膜材料。(3) mixing and stirring the polyurethane prepolymer 2 obtained in step (2) and the maleimide-grafted cellulose nanocrystals, and extruding to obtain the microporous repairable TPU film material.
优选地，步骤(1)所述反应的温度为100-120℃，例如可以是100℃、102℃、105℃、108℃、110℃、112℃、115℃、118℃、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 100-120°C, such as 100°C, 102°C, 105°C, 108°C, 110°C, 112°C, 115°C, 118°C, 120°C, etc., so The reaction time is 2-4h, for example, it can be 2h, 2.5h, 3h, 3.5h, 4h and the like.
优选地，步骤(2)所述反应的温度为80-90℃，例如可以是80℃、82℃、84℃、86℃、88℃、90℃等，所述反应的时间为1-3h，例如可以是1h、1.5h、2h、2.5h、3h等。Preferably, the temperature of the reaction in step (2) is 80-90°C, such as 80°C, 82°C, 84°C, 86°C, 88°C, 90°C, etc., and the reaction time is 1-3h, For example, it can be 1h, 1.5h, 2h, 2.5h, 3h and so on.
优选地，步骤(3)所述混合搅拌的温度为60-70℃，例如可以是60℃、62℃、64℃、66℃、68℃、70℃等，所述混合搅拌的时间为30-60min，例如可以是 30min、35min、40min、45min、50min、55min、60min等。Preferably, the temperature of the mixing and stirring in step (3) is 60-70°C, such as 60°C, 62°C, 64°C, 66°C, 68°C, 70°C, etc., and the mixing and stirring time is 30- 60min, for example, can be 30min, 35min, 40min, 45min, 50min, 55min, 60min 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，所述双螺杆挤出机混合段温度为130-150℃，例如可以是130℃、135℃、140℃、145℃、150℃等，挤出段温度为180-190℃，例如可以是180℃、182℃、184℃、186℃、188℃、190℃等，螺杆转速为300-500r/min，例如可以是300r/min、350r/min、400r/min、450r/min、500r/min等。Preferably, the extrusion molding in step (3) is performed by a twin-screw extruder, and the temperature of the mixing section of the twin-screw extruder is 130-150°C, for example, 130°C, 135°C, 140°C, 145°C , 150°C, etc., the extrusion temperature is 180-190°C, for example, it can be 180°C, 182°C, 184°C, 186°C, 188°C, 190°C, etc., and the screw speed is 300-500r/min, for example, it can be 300r /min, 350r/min, 400r/min, 450r/min, 500r/min, etc.
优选地，所述微孔可修复TPU薄膜材料的制备方法包括以下步骤：Preferably, the preparation method of the microporous repairable TPU film material comprises the following steps:
(1)将聚酯多元醇、聚醚多元醇、二异氰酸酯、糠胺接枝改性的碱木质素和催化剂混合，在100-120℃反应2-4h，得到聚氨酯预聚物一；(1) mixing polyester polyol, polyether polyol, diisocyanate, and furfurylamine graft-modified alkali lignin and catalyst, and reacting at 100-120° C. for 2-4 hours to obtain polyurethane prepolymer one;
(2)将步骤(1)得到的聚氨酯预聚物、硫醚扩链剂和硼酸混合，在80-90℃反应1-3h，得到聚氨酯预聚物二；(2) mixing the polyurethane prepolymer obtained in step (1), the thioether chain extender and boric acid, and reacting at 80-90° C. for 1-3 hours to obtain polyurethane prepolymer II;
(3)将步骤(2)得到的聚氨酯预聚物二、马来酰亚胺接枝纤维素纳米晶和润滑剂在60-70℃混合搅拌30-60min，采用双螺杆挤出机挤出，所述双螺杆挤出机混合段温度为130-150℃，挤出段温度为180-190℃，螺杆转速为300-500r/min，再利用单螺杆挤出流延成膜或吹塑成膜，得到所述微孔可修复TPU薄膜材料。(3) mixing and stirring the polyurethane prepolymer II, maleimide-grafted cellulose nanocrystals and lubricant obtained in step (2) at 60-70 ° C for 30-60 min, and extruding with a twin-screw extruder, The temperature of the mixing section of the twin-screw extruder is 130-150°C, the temperature of the extrusion section is 180-190°C, the screw speed is 300-500r/min, and then the single-screw extruder is used to extrude and cast a film or blow a film. , to obtain the microporous repairable TPU film material.
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、聚醚多元醇、二异氰酸酯、硫醚扩链剂、硼酸、催化剂、糠胺接枝改性的碱木质素和马来酰亚胺接枝纤维素纳米晶制备得到，在保证TPU薄膜材料具有良好的力学性能基础上，兼顾了自修复性能和修复条件温和的特点，尤其对于薄膜做出的孔洞修复性能优异，解决以往自修复材料存在的力学性能和自修复性能不兼容的问题；(1) The TPU film material of the present invention is composed of an appropriate proportion of polyester polyol, polyether polyol, diisocyanate, thioether chain extender, boric acid, catalyst, furfurylamine graft-modified alkali lignin and maleic acid The imide-grafted cellulose nanocrystals are prepared. On the basis of ensuring the good mechanical properties of the TPU film material, it takes into account the characteristics of self-healing performance and mild repair conditions, especially for the excellent hole repair performance of the film. The incompatibility of mechanical properties and self-healing properties of self-healing materials;
(2)本发明所述TPU薄膜材料拉伸强度在40MPa以上，断裂伸长率高达 600％以上；且对于做出的直径在2cm以下的孔洞由极强的可修复能力，在40-60℃的升温处理后，TPU薄膜材料上的孔洞即可自动愈合，自修复效率高达98％以上，愈合后的TPU薄膜材料拉伸强度仍能维持在40MPa以上，断裂伸长率仍能维持在600％以上。(2) The tensile strength of the TPU film material of the present invention is above 40 MPa, and the elongation at break is as high as 600% or more; and the holes with a diameter of less than 2 cm are extremely repairable and can be repaired at 40-60 ° C. After the high temperature treatment, the holes on the TPU film material can be automatically healed, and the self-healing efficiency is as high as 98%. above.
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.
下述实施例中的糠胺接枝改性的碱木质素和马来酰亚胺接枝纤维素纳米晶由制备例1和制备例2制备得到，其他组分均为市售产品。The furfurylamine graft-modified alkali lignin and maleimide-grafted cellulose nanocrystals in the following examples are prepared from Preparation Example 1 and Preparation Example 2, and other components are commercially available products.
制备例1Preparation Example 1
本制备例提供一种糠胺接枝改性的碱木质素，所述糠胺接枝改性的碱木质素的制备方法包括以下步骤：This preparation example provides a furfurylamine graft-modified alkali lignin, and the preparation method of the furfurylamine graft-modified alkali lignin comprises the following steps:
(1)将50份木质素和50份的30wt％的氢氧化钠水溶液混合，再加入100份的40wt％的乙二醛水溶液混合，在60℃下反应4h，过滤，得到滤渣；(1) mixing 50 parts of lignin with 50 parts of a 30wt% sodium hydroxide aqueous solution, then adding 100 parts of a 40wt% glyoxal aqueous solution to mix, reacting at 60° C. for 4h, and filtering to obtain a filter residue;
(2)将20份滤渣和30份六亚甲基二异氰酸酯溶于200份溶于DMSO中，再加入0.001份二月桂酸二丁基锡后，在60℃下反应2h，再滴加30份糠胺，滴加完毕后，在25℃下反应1h，将反应液滴加入500份乙醚中沉淀，将沉淀过滤、清洗并干燥，得到所述糠胺接枝改性的碱木质素。(2) Dissolve 20 parts of filter residue and 30 parts of hexamethylene diisocyanate in 200 parts of DMSO, then add 0.001 part of dibutyltin dilaurate, react at 60°C for 2 hours, and then dropwise add 30 parts of furfurylamine , after the dropwise addition, the reaction was carried out at 25° C. for 1 h, the reaction droplets were added to 500 parts of ether for precipitation, and the precipitation was filtered, washed and dried to obtain the furfurylamine graft-modified alkali lignin.
制备例2Preparation Example 2
本制备例提供一种马来酰亚胺接枝纤维素纳米晶，所述马来酰亚胺接枝纤维素纳米晶的制备方法为：将30份的10wt％的纤维素纳米晶水分散体、10份的6-马来酰亚胺己酸和10份去离子水混合均匀，加热至100℃反应6h，过滤、 旋蒸，得到所述马来酰亚胺接枝纤维素纳米晶。This preparation example provides a maleimide-grafted cellulose nanocrystal, and the preparation method of the maleimide-grafted cellulose nanocrystal is as follows: 30 parts of 10wt% cellulose nanocrystal water dispersion , 10 parts of 6-maleimide caproic acid and 10 parts of deionized water are mixed evenly, heated to 100° C. to react for 6 hours, filtered, and rotary steamed to obtain the maleimide-grafted cellulose nanocrystals.
实施例1Example 1
本实施例提供一种微孔可修复TPU薄膜材料，所述微孔可修复TPU薄膜材料的制备方法包括以下步骤：The present embodiment provides a microporous repairable TPU film material, and the preparation method of the microporous repairable TPU film material includes the following steps:
(1)将50份的聚丁二酸丁二醇酯(重均分子量为2000)、10份的聚四氢呋喃二醇(重均分子量为2000)、30份的六亚甲基二异氰酸酯、3份的糠胺接枝改性的碱木质素和0.05份的二月桂酸二丁基锡混合，在110℃反应3h，得到聚氨酯预聚物一；(1) 50 parts of polybutylene succinate (weight average molecular weight of 2000), 10 parts of polytetrahydrofuran diol (weight average molecular weight of 2000), 30 parts of hexamethylene diisocyanate, 3 parts of The graft-modified alkali lignin of furfuryl amine and 0.05 part of dibutyltin dilaurate were mixed and reacted at 110 °C for 3 h to obtain polyurethane prepolymer one;
(2)将步骤(1)得到的聚氨酯预聚物、5份的4，4′-二氨基二苯二硫醚和1份的硼酸混合，在85℃反应2h，得到聚氨酯预聚物二；(2) mixing the polyurethane prepolymer obtained in step (1), 5 parts of 4,4'-diaminodiphenyl disulfide and 1 part of boric acid, and reacting at 85° C. for 2 hours to obtain polyurethane prepolymer II;
(3)将步骤(2)得到的聚氨酯预聚物二、2份的马来酰亚胺接枝纤维素纳米晶和0.2份的单硬脂酸甘油酯在65℃混合搅拌40min，采用双螺杆挤出机挤出，所述双螺杆挤出机混合段温度为140℃，挤出段温度为185℃，螺杆转速为400r/min，再利用单螺杆挤出流延成膜，得到所述微孔可修复TPU薄膜材料。(3) Two parts of the polyurethane prepolymer obtained in step (2), 2 parts of maleimide-grafted cellulose nanocrystals and 0.2 part of glycerol monostearate were mixed and stirred at 65° C. for 40 minutes, and a twin screw was used. Extruder extruder, the temperature of the mixing section of the twin-screw extruder is 140 ° C, the temperature of the extrusion section is 185 ° C, and the screw speed is 400 r/min, and then the single-screw extrusion is used to cast a film to obtain the micro Hole repairable TPU film material.
实施例2Example 2
本实施例提供一种微孔可修复TPU薄膜材料，所述微孔可修复TPU薄膜材料的制备方法包括以下步骤：The present embodiment provides a microporous repairable TPU film material, and the preparation method of the microporous repairable TPU film material includes the following steps:
(1)将52份的聚丁二酸丁二醇酯(重均分子量为2000)、12份的四氢呋喃-氧化乙烯共聚物二醇(重均分子量为2000)、32份的六亚甲基二异氰酸酯、2份的糠胺接枝改性的碱木质素和0.06份的二月桂酸二丁基锡混合，在120℃反应3.5h，得到聚氨酯预聚物一；(1) 52 parts of polybutylene succinate (weight average molecular weight: 2000), 12 parts of tetrahydrofuran-ethylene oxide copolymer diol (weight average molecular weight: 2000), 32 parts of hexamethylene diol Isocyanate, 2 parts of furfurylamine graft-modified alkali lignin and 0.06 part of dibutyltin dilaurate were mixed, and reacted at 120°C for 3.5h to obtain polyurethane prepolymer 1;
(2)将步骤(1)得到的聚氨酯预聚物、4份的2，2′-二氨基二苯二硫醚和1.5份的硼酸混合，在80℃反应3h，得到聚氨酯预聚物二；(2) mixing the polyurethane prepolymer obtained in step (1), 4 parts of 2,2′-diaminodiphenyldisulfide and 1.5 parts of boric acid, and reacting at 80° C. for 3 hours to obtain polyurethane prepolymer II;
(3)将步骤(2)得到的聚氨酯预聚物二、3份的马来酰亚胺接枝纤维素纳米晶和0.2份的硬脂酸酰胺在70℃混合搅拌30min，采用双螺杆挤出机挤出，所述双螺杆挤出机混合段温度为130℃，挤出段温度为180℃，螺杆转速为300r/min，再利用单螺杆挤出流延成膜，得到所述微孔可修复TPU薄膜材料。(3) Two and three parts of maleimide-grafted cellulose nanocrystals of the polyurethane prepolymer obtained in step (2) and 0.2 part of stearic acid amide were mixed and stirred at 70° C. for 30 minutes, and extruded by twin-screw. The temperature of the mixing section of the twin-screw extruder is 130 °C, the temperature of the extrusion section is 180 °C, the screw speed is 300 r/min, and then the single-screw extrusion is used to cast a film to obtain the microporous Repair TPU film material.
实施例3Example 3
本实施例提供一种微孔可修复TPU薄膜材料，所述微孔可修复TPU薄膜材料的制备方法包括以下步骤：The present embodiment provides a microporous repairable TPU film material, and the preparation method of the microporous repairable TPU film material includes the following steps:
(1)将46份的聚己二酸丁二醇酯(重均分子量为2000)、8份的四氢呋喃-氧化乙烯共聚物二醇(重均分子量为2000)、28份的六亚甲基二异氰酸酯、4份的糠胺接枝改性的碱木质素和0.05份的二月桂酸二丁基锡混合，在100℃反应4h，得到聚氨酯预聚物一；(1) 46 parts of polybutylene adipate (weight average molecular weight of 2000), 8 parts of tetrahydrofuran-ethylene oxide copolymer diol (weight average molecular weight of 2000), 28 parts of hexamethylene diol Isocyanate, 4 parts of furfurylamine graft-modified alkali lignin and 0.05 part of dibutyltin dilaurate were mixed, and reacted at 100°C for 4h to obtain polyurethane prepolymer 1;
(2)将步骤(1)得到的聚氨酯预聚物、8份的2，2′-二氨基二苯二硫醚和1.2份的硼酸混合，在90℃反应1h，得到聚氨酯预聚物二；(2) mixing the polyurethane prepolymer obtained in step (1), 8 parts of 2,2'-diaminodiphenyl disulfide and 1.2 parts of boric acid, and reacting at 90° C. for 1 h to obtain polyurethane prepolymer II;
(3)将步骤(2)得到的聚氨酯预聚物二、1.5份的马来酰亚胺接枝纤维素纳米晶和0.2份的单硬脂酸甘油酯在70℃混合搅拌30min，采用双螺杆挤出机挤出，所述双螺杆挤出机混合段温度为140℃，挤出段温度为190℃，螺杆转速为500r/min，再利用单螺杆挤出流延成膜，得到所述微孔可修复TPU薄膜材料。(3) The polyurethane prepolymer 2 obtained in step (2), 1.5 parts of maleimide-grafted cellulose nanocrystals and 0.2 parts of glycerol monostearate were mixed and stirred at 70° C. for 30 minutes, using twin screw Extruder extruder, the temperature of the mixing section of the twin-screw extruder is 140 ° C, the temperature of the extrusion section is 190 ° C, the screw speed is 500 r/min, and then the single-screw extrusion is used to cast a film to obtain the micro Hole repairable TPU film material.
实施例4Example 4
本实施例提供一种微孔可修复TPU薄膜材料，所述微孔可修复TPU薄膜材料的制备方法包括以下步骤：The present embodiment provides a microporous repairable TPU film material, and the preparation method of the microporous repairable TPU film material includes the following steps:
(1)将50份的聚丁二酸丁二醇酯(重均分子量为2000)、10份的聚四氢呋喃二醇(重均分子量为2000)、30份的六亚甲基二异氰酸酯、2份的马来酰亚胺接枝纤维素纳米晶和0.05份的二月桂酸二丁基锡混合，在110℃反应3h， 得到聚氨酯预聚物一；(1) 50 parts of polybutylene succinate (weight average molecular weight: 2000), 10 parts of polytetrahydrofuran diol (weight average molecular weight: 2000), 30 parts of hexamethylene diisocyanate, 2 parts The maleimide-grafted cellulose nanocrystals were mixed with 0.05 part of dibutyltin dilaurate, and reacted at 110° C. for 3 hours to obtain polyurethane prepolymer 1;
(2)将步骤(1)得到的聚氨酯预聚物、5份的4，4′-二氨基二苯二硫醚和1份的硼酸混合，在85℃反应2h，得到聚氨酯预聚物二；(2) mixing the polyurethane prepolymer obtained in step (1), 5 parts of 4,4'-diaminodiphenyl disulfide and 1 part of boric acid, and reacting at 85° C. for 2 hours to obtain polyurethane prepolymer II;
(3)将步骤(2)得到的聚氨酯预聚物二、3份的糠胺接枝改性的碱木质素和0.2份的单硬脂酸甘油酯在65℃混合搅拌40min，采用双螺杆挤出机挤出，所述双螺杆挤出机混合段温度为140℃，挤出段温度为185℃，螺杆转速为400r/min，再利用单螺杆挤出流延成膜，得到所述微孔可修复TPU薄膜材料。(3) 2 parts of the polyurethane prepolymer obtained in step (2), 3 parts of furfurylamine graft-modified alkali lignin and 0.2 part of glycerol monostearate were mixed and stirred at 65°C for 40min, and the twin-screw extrusion was adopted. Extruding from the machine, the temperature of the mixing section of the twin-screw extruder is 140 ° C, the temperature of the extrusion section is 185 ° C, and the screw speed is 400 r/min, and then the single-screw extrusion is used to cast a film to obtain the micropores. Repairable TPU film material.
实施例5Example 5
本实施例提供一种微孔可修复TPU薄膜材料，所述微孔可修复TPU薄膜材料的制备方法包括以下步骤：The present embodiment provides a microporous repairable TPU film material, and the preparation method of the microporous repairable TPU film material includes the following steps:
(1)将50份的聚丁二酸丁二醇酯(重均分子量为2000)、10份的聚四氢呋喃二醇(重均分子量为2000)、30份的六亚甲基二异氰酸酯、3份的糠胺接枝改性的碱木质素、2份的马来酰亚胺接枝纤维素纳米晶和0.05份的二月桂酸二丁基锡混合，在110℃反应3h，得到聚氨酯预聚物一；(1) 50 parts of polybutylene succinate (weight average molecular weight of 2000), 10 parts of polytetrahydrofuran diol (weight average molecular weight of 2000), 30 parts of hexamethylene diisocyanate, 3 parts of The furfuryl amine graft-modified alkali lignin, 2 parts of maleimide-grafted cellulose nanocrystals and 0.05 part of dibutyltin dilaurate were mixed and reacted at 110 °C for 3 h to obtain polyurethane prepolymer 1;
(2)将步骤(1)得到的聚氨酯预聚物、5份的4，4′-二氨基二苯二硫醚和1份的硼酸混合，在85℃反应2h，得到聚氨酯预聚物二；(2) mixing the polyurethane prepolymer obtained in step (1), 5 parts of 4,4'-diaminodiphenyl disulfide and 1 part of boric acid, and reacting at 85° C. for 2 hours to obtain polyurethane prepolymer II;
(3)将步骤(2)得到的聚氨酯预聚物二和0.2份的单硬脂酸甘油酯在65℃混合搅拌40min，采用双螺杆挤出机挤出，所述双螺杆挤出机混合段温度为140℃，挤出段温度为185℃，螺杆转速为400r/min，再利用单螺杆挤出流延成膜，得到所述微孔可修复TPU薄膜材料。(3) The polyurethane prepolymer obtained in step (2) and 0.2 part of glycerol monostearate were mixed and stirred at 65° C. for 40 minutes, and extruded by a twin-screw extruder. The mixing section of the twin-screw extruder The temperature is 140° C., the temperature of the extrusion section is 185° C., the screw speed is 400 r/min, and the single-screw extrusion casting film is used to obtain the microporous repairable TPU film material.
实施例6Example 6
本实施例提供一种微孔可修复TPU薄膜材料，与实施例1的区别仅在于，将所述聚四氢呋喃二醇(重均分子量为2000)替换为聚氧化丙烯二醇(重均分 子量为2000)，其他组分含量及制备方法同实施例1。This embodiment provides a microporous repairable TPU film material. The only difference from Embodiment 1 is that the polytetrahydrofuran diol (weight average molecular weight is 2000) is replaced with polyoxypropylene glycol (weight average molecular weight is 2000) ), the content of other components and the preparation method are the same as in Example 1.
实施例7Example 7
本实施例提供一种微孔可修复TPU薄膜材料，与实施例1的区别仅在于，将六亚甲基二异氰酸酯替换为异佛尔酮二异氰酸酯，其他组分含量及制备方法同实施例1。This embodiment provides a microporous repairable TPU film material. The only difference from Embodiment 1 is that hexamethylene diisocyanate is replaced with isophorone diisocyanate, and the contents and preparation methods of other components are the same as those in Embodiment 1. .
实施例8Example 8
本实施例提供一种微孔可修复TPU薄膜材料，与实施例1的区别仅在于，所述微孔可修复TPU薄膜材料的制备原料中不添加润滑剂，其他组分含量及制备方法同实施例1。This embodiment provides a microporous repairable TPU film material. The only difference from Example 1 is that no lubricant is added to the preparation raw material of the microporous repairable TPU film material, and the contents of other components and the preparation method are the same as the implementation. example 1.
对比例1Comparative Example 1
本对比例提供一种TPU薄膜材料，与实施例1的区别仅在于，步骤(2)中不再添加4，4′-二氨基二苯二硫醚，将硼酸含量增至6份，其他组分含量及制备方法同实施例1。This comparative example provides a TPU film material. The only difference from Example 1 is that in step (2), 4,4'-diaminodiphenyl disulfide is no longer added, and the content of boric acid is increased to 6 parts. The content and preparation method are the same as those in Example 1.
对比例2Comparative Example 2
本对比例提供一种TPU薄膜材料，与实施例1的区别仅在于，步骤(2)中不再添加硼酸，将4，4′-二氨基二苯二硫醚含量增至6份，其他组分含量及制备方法同实施例1。This comparative example provides a TPU film material. The only difference from Example 1 is that in step (2), no boric acid is added, and the content of 4,4'-diaminodiphenyldisulfide is increased to 6 parts. The content and preparation method are the same as those in Example 1.
对比例3Comparative Example 3
本对比例提供一种TPU薄膜材料，与实施例1的区别仅在于，将4，4′-二氨基二苯二硫醚替换为乙二醇，其他组分含量及制备方法同实施例1。This comparative example provides a TPU film material, which differs from Example 1 only in that 4,4'-diaminodiphenyldisulfide is replaced with ethylene glycol, and the contents and preparation methods of other components are the same as those of Example 1.
对比例4Comparative Example 4
本对比例提供一种TPU薄膜材料，与实施例1的区别仅在于，步骤(2)中4，4′-二氨基二苯二硫醚含量减至3份，硼酸含量增至6份，其他组分含量及 制备方法同实施例1。This comparative example provides a TPU film material, which differs from Example 1 only in that the content of 4,4'-diaminodiphenyldisulfide in step (2) is reduced to 3 parts, the content of boric acid is increased to 6 parts, and other Component content and preparation method are the same as in Example 1.
对比例5Comparative Example 5
本对比例提供一种TPU薄膜材料，与实施例1的区别仅在于，步骤(1)中不再添加糠胺接枝改性的碱木质素，步骤(3)中马来酰亚胺接枝纤维素纳米晶含量增至5份，其他组分含量及制备方法同实施例1。This comparative example provides a TPU film material, the only difference from Example 1 is that in step (1), furfurylamine graft-modified alkali lignin is no longer added, and in step (3), maleimide is grafted The content of cellulose nanocrystals was increased to 5 parts, and the content of other components and the preparation method were the same as those of Example 1.
对比例6Comparative Example 6
本对比例提供一种TPU薄膜材料，与实施例1的区别仅在于，步骤(3)中不再添加马来酰亚胺接枝纤维素纳米晶，步骤(1)中糠胺接枝改性的碱木质素含量增至5份，其他组分含量及制备方法同实施例1。This comparative example provides a TPU film material, which differs from Example 1 only in that in step (3), maleimide is not added to graft cellulose nanocrystals, and in step (1), furfurylamine is grafted and modified The content of alkali lignin was increased to 5 parts, and the content of other components and the preparation method were the same as those of Example 1.
对比例7Comparative Example 7
本对比例提供一种TPU薄膜材料，与实施例1的区别仅在于，步骤(1)中不再添加聚丁二酸丁二醇酯，而聚四氢呋喃二醇含量增至60份，其他组分含量及制备方法同实施例1。This comparative example provides a TPU film material, the only difference from Example 1 is that polybutylene succinate is no longer added in step (1), and the content of polytetrahydrofurandiol is increased to 60 parts, and other components The content and preparation method are the same as those in Example 1.
对比例8Comparative Example 8
本对比例提供一种TPU薄膜材料，与实施例1的区别仅在于，步骤(1)中不再添加聚四氢呋喃二醇，而聚丁二酸丁二醇酯含量增至60份，其他组分含量及制备方法同实施例1。This comparative example provides a TPU film material, the only difference from Example 1 is that polytetrahydrofuran diol is no longer added in step (1), and the content of polybutylene succinate is increased to 60 parts, and other components The content and preparation method are the same as those in Example 1.
性能测试Performance Testing
对上述实施例1-8制备得到的微孔可修复TPU薄膜材料和对比例1-8制备得到的TPU薄膜材料进行各项性能测试。其中，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；自修复性能测试方法为：分别将各薄膜材料做一个2mm的孔，然后将薄膜至于50℃下烘烤，观察材料表面的自愈合情况，并测定愈合后各薄膜材料的拉伸 强度和断裂伸长率。Various performance tests were carried out on the microporous repairable TPU film materials prepared in the above examples 1-8 and the TPU film materials prepared in the comparative examples 1-8. Among them, the tensile strength of each film material is tested according to GB/T1040.3-2006, and the elongation at break of each film material is tested according to GB/T 1040.1-2006; the self-healing performance test method is: make a 2mm hole, and then bake the film at 50°C to observe the self-healing of the material surface, and measure the tensile strength and elongation at break of each film material after healing.
具体测试结果如表1所示(其中，“-”代表无法愈合，参数无法测试)：The specific test results are shown in Table 1 (wherein "-" represents failure to heal, and the parameters cannot be tested):
表1Table 1
Figure PCTCN2020140455-appb-000002
Figure PCTCN2020140455-appb-000002
Figure PCTCN2020140455-appb-000003
Figure PCTCN2020140455-appb-000003
由表1测试数据可知，本发明所述TPU薄膜材料拉伸强度在40MPa以上，断裂伸长率高达600％以上；且对于做出的直径在2cm以下的孔洞由极强的可修复能力，在40-60℃的升温处理后，TPU薄膜材料上的孔洞即可自动愈合，自修复效率高达98％以上，愈合后的TPU薄膜材料拉伸强度仍能维持在40MPa以上，断裂伸长率仍能维持在600％以上。说明本发明在保证TPU薄膜材料具有良好的力学性能基础上，兼顾了自修复性能和修复条件温和的特点，尤其对于薄膜做出的孔洞修复性能优异，解决以往自修复材料存在的力学性能和自修复性能不兼容的问题。It can be seen from the test data in Table 1 that the tensile strength of the TPU film material of the present invention is above 40MPa, and the elongation at break is as high as 600% or more; After the heating treatment of 40-60℃, the holes on the TPU film material can be healed automatically, and the self-healing efficiency is as high as 98%. The tensile strength of the healed TPU film material can still be maintained above 40MPa, and the elongation at break can still be maintained above 600%. It shows that the present invention takes into account the characteristics of self-healing performance and mild repair conditions on the basis of ensuring that the TPU film material has good mechanical properties, especially for the excellent hole repairing performance made by the film, and solves the mechanical properties and self-healing properties of the previous self-healing materials. Fix performance incompatibility issues.
由实施例1和实施例4、5的对比可知，糠胺接枝改性的碱木质素和马来酰亚胺接枝纤维素纳米晶的添加顺序对本发明制备得到的TPU薄膜材料结构有一定影响，按照本发明所述制备方法制备得到的TPU薄膜材料的力学性能更强、修复能力更好。由实施例1和实施例6、7的对比可知，采用本发明优选的聚醚多元醇和二异氰酸酯，制备得到的TPU薄膜材料力学性能和自修复性能提升更为明显。From the comparison of Example 1 and Examples 4 and 5, it can be seen that the order of addition of furfurylamine graft-modified alkali lignin and maleimide grafted cellulose nanocrystals has a certain effect on the structure of the TPU film material prepared by the present invention. Influence, the TPU film material prepared according to the preparation method of the present invention has stronger mechanical properties and better repairing ability. It can be seen from the comparison between Example 1 and Examples 6 and 7 that the mechanical properties and self-healing properties of the prepared TPU film material are improved more obviously by using the preferred polyether polyol and diisocyanate of the present invention.
由实施例1和对比例1-3的对比可知，本发明通过在聚氨酯的主链中引入二硫键提高链段运动能力，同时利用硼酸构建的硼酸酯键形成可逆交联网络，使聚氨酯内部形成交联网络结构，得到高修复效率的可修复TPU薄膜材料，缺少硫醚扩链剂和硼酸中任一种制备得到的的TPU薄膜材料均没有修复能力，孔洞无法愈合。From the comparison between Example 1 and Comparative Examples 1-3, it can be seen that the present invention improves the mobility of segments by introducing disulfide bonds into the main chain of the polyurethane, and at the same time uses the boric acid ester bonds constructed by boronic acid to form a reversible cross-linked network, so that the polyurethane A cross-linked network structure is formed inside, and a repairable TPU film material with high repair efficiency is obtained. The TPU film material prepared without either sulfide chain extender or boric acid has no repair ability, and the pores cannot be healed.
由实施例1和对比例4的对比可知，硫醚扩链剂和硼酸含量在本申请范围内时，制备得到的TPU薄膜材料力学性能和自修复性能能得到进一步提升。It can be seen from the comparison between Example 1 and Comparative Example 4 that when the content of thioether chain extender and boric acid is within the scope of the application, the mechanical properties and self-healing properties of the prepared TPU film material can be further improved.
由实施例1和对比例5、6的对比可知，糠胺接枝改性的碱木质素和马来酰 亚胺接枝纤维素纳米晶相互配合，具有协同增效的作用，不仅可以进一步提高聚氨酯的自修复的能力还可以改善聚氨酯的机械性能。From the comparison between Example 1 and Comparative Examples 5 and 6, it can be seen that the alkali lignin grafted with furfurylamine and the maleimide grafted cellulose nanocrystals cooperate with each other and have a synergistic effect, which can not only further improve the The self-healing ability of polyurethane can also improve the mechanical properties of polyurethane.
由实施例1和对比例7、8的对比可知，本发明所述多元醇选择聚酯多元醇和聚醚多元醇相互配合，能够更好地在在聚氨酯的主链中引入二硫键，并构建的硼酸酯键形成可逆交联网络，制备得到的TPU薄膜材料力学性能和自修复性能提升更为明显。From the comparison between Example 1 and Comparative Examples 7 and 8, it can be seen that the polyol of the present invention selects polyester polyol and polyether polyol to cooperate with each other, which can better introduce disulfide bonds in the main chain of polyurethane, and construct The boronate bond formed a reversible cross-linked network, and the mechanical properties and self-healing properties of the prepared TPU film material were improved more obviously.
申请人声明，本发明通过上述实施例来说明所述微孔可修复TPU薄膜材料及其制备方法，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 microporous repairable TPU film material and its preparation method by the above-mentioned examples, but the present invention is not limited to the above-mentioned examples, that is to say, it does not mean that the present invention can only be implemented by relying on the above-mentioned examples. . Those skilled in the art should understand that any improvement to 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. 一种微孔可修复TPU薄膜材料，其特征在于，所述微孔可修复TPU薄膜材料的制备原料按重量份数计包括如下组分：A microporous repairable TPU film material is characterized in that, the preparation raw materials of the microporous repairable TPU film material include the following components in parts by weight:
    Figure PCTCN2020140455-appb-100001
    Figure PCTCN2020140455-appb-100001
  2. 根据权利要求1所述的微孔可修复TPU薄膜材料，其特征在于，所述聚酯多元醇的重均分子量为1000-3000；The microporous repairable TPU film material according to claim 1, wherein the weight average molecular weight of the polyester polyol is 1000-3000;
    优选地，所述聚酯多元醇选自聚丁二酸丁二醇酯、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 is selected from polybutylene succinate, polybutylene adipate, polyhexamethylene adipate or polybutylene glycol adipate any one or a combination of at least two.
  3. 根据权利要求1或2所述的微孔可修复TPU薄膜材料，其特征在于，所述聚醚多元醇的重均分子量为1000-3000；The microporous repairable TPU film material according to claim 1 or 2, wherein the weight average molecular weight of the polyether polyol is 1000-3000;
    优选地，所述聚醚多元醇选自聚氧化丙烯二醇、聚氧化乙烯二醇、聚氧化丙烯聚醚三醇、氧化丙烯-氧化乙烯共聚三醇、聚四氢呋喃二醇或四氢呋喃-氧化乙烯共聚物二醇中的任意一种或至少两种的组合，优选为聚四氢呋喃二醇和/或四氢呋喃-氧化乙烯共聚物二醇。Preferably, the polyether polyol is selected from the group consisting of polyoxypropylene diol, polyoxyethylene diol, polyoxypropylene polyether triol, oxypropylene-ethylene oxide copolymer triol, polytetrahydrofuran diol or tetrahydrofuran-ethylene oxide copolymer Any one or a combination of at least two of the diols, preferably polytetrahydrofuran diol and/or tetrahydrofuran-ethylene oxide copolymer diol.
  4. 根据权利要求1-3中任一项所述的微孔可修复TPU薄膜材料，其特征在于，所述二异氰酸酯选自异佛尔酮二异氰酸酯、甲苯二异氰酸酯、二苯基甲烷二异氰酸酯或六亚甲基二异氰酸酯中的任意一种或至少两种的组合，优选为 六亚甲基二异氰酸酯。The microporous repairable TPU film material according to any one of claims 1-3, wherein the diisocyanate is selected from isophorone diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate or hexamethylene diisocyanate Any one or a combination of at least two of the methylene diisocyanates is preferably hexamethylene diisocyanate.
  5. 根据权利要求1-4中任一项所述的微孔可修复TPU薄膜材料，其特征在于，所述硫醚扩链剂选自4，4′-二氨基二苯二硫醚、2，2′-二氨基二苯二硫醚、3，3′-二羟基二苯二硫醚、4，4′-二羟基二苯二硫醚或双(2-羟乙基)二硫化物中的任意一种或至少两种的组合。The microporous repairable TPU film material according to any one of claims 1-4, wherein the thioether chain extender is selected from 4,4′-diaminodiphenyldisulfide, 2,2 Any of '-diaminodiphenyldisulfide, 3,3'-dihydroxydiphenyldisulfide, 4,4'-dihydroxydiphenyldisulfide or bis(2-hydroxyethyl)disulfide one or a combination of at least two.
  6. 根据权利要求1-5中任一项所述的微孔可修复TPU薄膜材料，其特征在于，所述催化剂选自二月桂酸二丁基锡、辛酸亚锡、辛酸钴或N-甲基吗啉中的任意一种或至少两种的组合。The microporous repairable TPU film material according to any one of claims 1-5, wherein the catalyst is selected from dibutyltin dilaurate, stannous octoate, cobalt octoate or N-methylmorpholine any one or a combination of at least two.
  7. 根据权利要求1-6中任一项所述的微孔可修复TPU薄膜材料，其特征在于，所述微孔可修复TPU薄膜材料的制备原料中还包括0.1-0.5份润滑剂；The microporous repairable TPU film material according to any one of claims 1-6, wherein the preparation raw material of the microporous repairable TPU film material further comprises 0.1-0.5 parts of lubricant;
    优选地，所述润滑剂选自单硬脂酸甘油酯、硬脂酸酰胺、乙撑双硬脂酸酰胺、E蜡或油酸酰胺中的任意一种或至少两种的组合。Preferably, the lubricant is selected from any one or a combination of at least two of glycerol monostearate, stearic acid amide, ethylene bis stearic acid amide, E wax or oleic acid amide.
  8. 根据权利要求1-7中任一项所述的微孔可修复TPU薄膜材料的制备方法，其特征在于，所述微孔可修复TPU薄膜材料的制备方法包括以下步骤：The preparation method of the microporous repairable TPU film material according to any one of claims 1-7, wherein the preparation method of the microporous repairable TPU film material comprises the following steps:
    (1)将聚酯多元醇、聚醚多元醇、二异氰酸酯、糠胺接枝改性的碱木质素和催化剂混合，反应得到聚氨酯预聚物一；(1) mixing polyester polyol, polyether polyol, diisocyanate, and furfurylamine graft-modified alkali lignin and catalyst, and reacting to obtain polyurethane prepolymer one;
    (2)将步骤(1)得到的聚氨酯预聚物、硫醚扩链剂和硼酸混合，反应得到聚氨酯预聚物二；(2) mixing the polyurethane prepolymer, thioether chain extender and boric acid obtained in step (1), and reacting to obtain polyurethane prepolymer II;
    (3)将步骤(2)得到的聚氨酯预聚物二和马来酰亚胺接枝纤维素纳米晶混合搅拌，挤出成型，得到所述微孔可修复TPU薄膜材料。(3) mixing and stirring the polyurethane prepolymer 2 obtained in step (2) and the maleimide-grafted cellulose nanocrystals, and extruding to obtain the microporous repairable TPU film material.
  9. 根据权利要求8所述的制备方法，其特征在于，步骤(1)所述反应的温度为100-120℃，所述反应的时间为2-4h；The preparation method according to claim 8, wherein the temperature of the reaction in step (1) is 100-120° C., and the time of the reaction is 2-4h;
    优选地，步骤(2)所述反应的温度为80-90℃，所述反应的时间为1-3h；Preferably, the temperature of the reaction in step (2) is 80-90° C., and the reaction time is 1-3h;
    优选地，步骤(3)所述混合搅拌的温度为60-70℃，所述混合搅拌的时间为30-60min；Preferably, the temperature of the mixing and stirring in step (3) is 60-70° C., and the time of the mixing and stirring is 30-60 min;
    优选地，步骤(3)所述挤出成型采用双螺杆挤出机进行，所述双螺杆挤出机混合段温度为130-150℃，挤出段温度为180-190℃，螺杆转速为300-500r/min。Preferably, the extrusion molding in step (3) is performed by a twin-screw extruder, the temperature of the mixing section of the twin-screw extruder is 130-150°C, the temperature of the extrusion section is 180-190°C, and the screw speed is 300°C -500r/min.
  10. 根据权利要求8或9所述的微孔可修复TPU薄膜材料的制备方法，其特征在于，所述微孔可修复TPU薄膜材料的制备方法包括以下步骤：The preparation method of the microporous repairable TPU film material according to claim 8 or 9, wherein the preparation method of the microporous repairable TPU film material comprises the following steps:
    (1)将聚酯多元醇、聚醚多元醇、二异氰酸酯、糠胺接枝改性的碱木质素和催化剂混合，在100-120℃反应2-4h，得到聚氨酯预聚物一；(1) mixing polyester polyol, polyether polyol, diisocyanate, and furfurylamine graft-modified alkali lignin and catalyst, and reacting at 100-120° C. for 2-4 hours to obtain polyurethane prepolymer one;
    (2)将步骤(1)得到的聚氨酯预聚物、硫醚扩链剂和硼酸混合，在80-90℃反应1-3h，得到聚氨酯预聚物二；(2) mixing the polyurethane prepolymer obtained in step (1), the thioether chain extender and boric acid, and reacting at 80-90° C. for 1-3 hours to obtain polyurethane prepolymer II;
    (3)将步骤(2)得到的聚氨酯预聚物二、马来酰亚胺接枝纤维素纳米晶和润滑剂在60-70℃混合搅拌30-60min，采用双螺杆挤出机挤出，所述双螺杆挤出机混合段温度为130-150℃，挤出段温度为180-190℃，螺杆转速为300-500r/min，再利用单螺杆挤出流延成膜或吹塑成膜，得到所述微孔可修复TPU薄膜材料。(3) mixing and stirring the polyurethane prepolymer 2, maleimide-grafted cellulose nanocrystals and lubricant obtained in step (2) at 60-70 ° C for 30-60 min, and extruding with a twin-screw extruder, The temperature of the mixing section of the twin-screw extruder is 130-150 °C, the temperature of the extrusion section is 180-190 °C, and the screw speed is 300-500 r/min, and then the single-screw extruder is used to extrude and cast a film or blow a film. , to obtain the microporous repairable TPU film material.
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