CN112341803B - Hyperbranched TPU hydrophilic film and preparation method thereof - Google Patents
Hyperbranched TPU hydrophilic film and preparation method thereof Download PDFInfo
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- CN112341803B CN112341803B CN202011349428.9A CN202011349428A CN112341803B CN 112341803 B CN112341803 B CN 112341803B CN 202011349428 A CN202011349428 A CN 202011349428A CN 112341803 B CN112341803 B CN 112341803B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 235000015112 vegetable and seed oil Nutrition 0.000 claims abstract description 37
- 241000208688 Eucommia Species 0.000 claims abstract description 36
- 238000003756 stirring Methods 0.000 claims abstract description 27
- 229920005862 polyol Polymers 0.000 claims abstract description 25
- 150000003077 polyols Chemical class 0.000 claims abstract description 25
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 18
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 238000005266 casting Methods 0.000 claims abstract description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 13
- 238000004321 preservation Methods 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 239000004970 Chain extender Substances 0.000 claims abstract description 10
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims abstract description 9
- 235000019253 formic acid Nutrition 0.000 claims abstract description 9
- 230000001678 irradiating effect Effects 0.000 claims abstract description 8
- -1 hydroxyl compound Chemical class 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims description 24
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 15
- 239000011521 glass Substances 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 238000002791 soaking Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 6
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 6
- 238000005191 phase separation Methods 0.000 claims description 6
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 5
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 3
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 claims description 2
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 claims description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 2
- 150000003384 small molecules Chemical group 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 2
- 125000005409 triarylsulfonium group Chemical group 0.000 claims description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 18
- 230000035699 permeability Effects 0.000 abstract description 13
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 239000012075 bio-oil Substances 0.000 abstract 1
- 230000008929 regeneration Effects 0.000 abstract 1
- 238000011069 regeneration method Methods 0.000 abstract 1
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 39
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 39
- 239000007789 gas Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 229920001971 elastomer Polymers 0.000 description 4
- 239000000806 elastomer Substances 0.000 description 4
- 238000001514 detection method Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000004154 testing of material Methods 0.000 description 2
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- 235000003913 Coccoloba uvifera Nutrition 0.000 description 1
- 241000208689 Eucommia ulmoides Species 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 240000008976 Pterocarpus marsupium Species 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000002457 bidirectional effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 150000002440 hydroxy compounds Chemical class 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 238000010128 melt processing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000010129 solution processing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- 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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/36—Hydroxylated esters of higher fatty acids
-
- 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
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
-
- 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
- C08J2375/14—Polyurethanes having carbon-to-carbon unsaturated bonds
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a hyperbranched TPU hydrophilic film and a preparation method thereof. The raw materials comprise diisocyanate, eucommia seed oil, formic acid, hydrogen peroxide, acetone, hydroxyl compounds and the like. The preparation method comprises the following steps: mixing and stirring the eucommia seed oil and formic acid, adding hydrogen peroxide, a hydroxyl compound and a photoinitiator, uniformly mixing, and irradiating under UV light for reaction to obtain eucommia seed oil-based polyol; dehydrating eucommia seed oil-based polyol, adding diisocyanate and a micromolecular chain extender, and carrying out heat preservation reaction to obtain TPU; and dissolving TPU to prepare a casting solution, and preparing the casting solution into a film. The hyperbranched bio-oil-based polyol is prepared by an ultraviolet light catalysis method, and the hydrophilic breathable TPU film is prepared by a wet film forming method. The invention not only has simple and controllable film forming process and is beneficial to large-scale production, but also fully utilizes biological resources, realizes the regeneration of raw materials and improves the hydrophilic air permeability of the TPU film.
Description
Technical Field
The invention relates to a hyperbranched thermoplastic polyurethane elastomer (TPU for short) hydrophilic film and a preparation method thereof, belonging to the technical field of functional high polymer materials.
Background
The TPU film is a novel, high-performance and environment-friendly film material which takes TPU particles as main raw materials, and can be divided into a polyester film and a polyether film in terms of chemical composition; from the production methods, melt processing and solution processing can be divided. The TPU film has the excellent characteristics of high strength, good toughness, wear resistance, cold resistance, oil resistance, degradability and the like, and can be used independently or used after being compounded with other materials. In recent years, TPU film products are widely used in the fields of footwear, waterproof moisture-permeable fabrics, high-grade handbags and leather products, air-filled bags and the like, but the problems of poor hydrophilic effect, poor durability, low utilization rate and the like of common TPU films still exist, so that the improvement of the hydrophilic performance of TPU becomes a key point by improving the structure of TPU to enable the TPU to have more hydrophilic groups.
Hyperbranched eucommia seed oil polyol is obtained by an ultraviolet catalysis method, and a hyperbranched hydrophilic film is prepared by a wet film forming method. Wet film formation is a process of phase separation of a polymer solution in a coagulation bath, and a bidirectional diffusion method is generated by utilizing the concentration difference of a solvent and a coagulant in the system. By ultraviolet catalysis and wet film formation, hydrophilic groups can be introduced from raw materials, the film has excellent hydrophilic performance, biological resources can be fully utilized, and dependence on petroleum resources is reduced. Therefore, the hyperbranched hydrophilic film with a large number of hydrophilic groups has excellent hydrophilic air permeability, and also has excellent performances of mechanical strength, corrosion resistance, friction resistance, aging resistance, cold resistance and the like
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the prior TPU film has the problems of poor hydrophilic effect, poor durability, low utilization rate, deficient resources and the like.
In order to solve the technical problems, the invention provides a hyperbranched TPU hydrophilic film which is characterized by comprising the following components in parts by weight:
preferably, the diisocyanate is at least one of isophorone diisocyanate (IPDI), Toluene Diisocyanate (TDI), 4' -diphenylmethane diisocyanate (MDI), Hexamethylene Diisocyanate (HDI), and 1, 5-Naphthalene Diisocyanate (NDI).
Preferably, the hydroxy compound is at least one of diethanolamine and isopropanol.
Preferably, the small-molecule chain extender is one or two of 1, 4-Butanediol (BDO) and 1, 6-Hexanediol (HDO).
Preferably, the photoinitiator is one or both of 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide (TPO) and triarylsulfonium salt (4- (phenylthio) phenyldiphenylsulfonium hexafluorophosphate) (TAS).
Preferably, the catalyst 1 is sodium hydroxide (NaOH) and sodium carbonate (Na)2CO3) At least one of; the catalyst 2 is at least one of dibutyltin dilaurate and stannous octoate.
Preferably, the solvent is N, N' -Dimethylformamide (DMF); the non-solvent is one or more of water, methanol, ethanol and isopropanol.
The invention also provides a preparation method of the eucommia seed oil modified hydrophilic thermoplastic polyurethane, which is characterized by comprising the following steps:
step 1): under the action of a catalyst 1, mixing and stirring the eucommia seed oil and formic acid, slowly adding hydrogen peroxide, continuously stirring, then adding a hydroxyl compound, stirring and standing, uniformly mixing with a photoinitiator dissolved in acetone, and irradiating and reacting under UV light to obtain eucommia seed oil-based polyol;
step 2): dehydrating eucommia seed oil-based polyol, adding diisocyanate and a catalyst 2 under the protection of nitrogen for heat preservation reaction, adding a small-molecular chain extender into a system, and performing heat preservation reaction to obtain TPU;
step 3): continuously stirring TPU and a solvent at 60-85 ℃ until the TPU and the solvent are completely dissolved to prepare a casting solution, standing the casting solution, sealing and removing bubbles, preparing a liquid film on a clean glass plate, and immediately soaking the glass plate in a non-solvent for 24-48 h; after the film casting solution is subjected to phase separation to form a film, transferring the prepared film from a glass plate to distilled water for soaking and extracting excessive solvent and non-solvent.
Preferably, the step 1) is specifically: stirring the eucommia seed oil and formic acid for 1-2 hours at the temperature of 30-50 ℃ under the action of a catalyst 1, then slowly adding hydrogen peroxide, continuously stirring for 6-8 hours at the temperature of 50-70 ℃, then adding a hydroxyl compound, stirring and standing, uniformly mixing with a photoinitiator dissolved in acetone, and irradiating and reacting for 3-8 min under the UV light of 400-475W to obtain the eucommia seed oil-based polyol with the hydroxyl value of 240-320 mgKOH/g.
Preferably, the step 2) is specifically: dehydrating the eucommia seed oil-based polyol at the temperature of 90-110 ℃ for 90-120 min, cooling to 65-85 ℃, adding diisocyanate and the catalyst 2 under the protection of nitrogen, reacting for 60-90 min under heat preservation, cooling to 40-60 ℃, adding the small molecular chain extender into the system, and reacting for 20-70 min under heat preservation.
According to the invention, the hydrophilic breathable TPU film is prepared by adopting a wet film forming process, and the hydrophilic TPU is prepared by adopting the bio-based polyol as a raw material, so that the energy problem is solved, and the product is endowed with excellent hydrophilic performance. The TPU film prepared by the process has excellent hydrophilic air permeability, is simple and controllable, and is beneficial to large-scale production.
Compared with the prior art, the beneficial effect of this technique is:
the hyperbranched TPU hydrophilic film is prepared by a wet film forming process. Hyperbranched eucommia seed oil-based polyol is prepared by utilizing the principle of molecular design, and is used as a raw material to synthesize hydrophilic polyester. The renewable material is used as a basic raw material, so that the prepared TPU film not only has excellent hydrophilic air permeability, but also has certain biodegradability, and the dependence on petroleum resources and the pollution to the environment are reduced. In addition, the TPU film prepared by the wet film forming technology has better hydrophilic air permeability, and the process is simple and controllable, and is beneficial to large-scale production. The preparation method of the hyperbranched TPU hydrophilic film provided by the invention is simple in process, low in cost and suitable for process production and development.
Further, the hydroxyl value of the hyperbranched eucommia seed oil-based polyol measured by a hydroxyl value titration analysis method is 240-320 mg KOH/g. According to the titration technique implemented on the contact angle tester, the contact angle is 20.3-43.5 degrees. The tensile strength is 28-45 Mpa and the elongation at break is 400-600% measured on a universal material testing machine. H2Permeability of 3X 10-8～5×10- 8mol·(m-2·s-1·Pa-1) (ii) a The gas permeation amount is 0.409-0.689 mm/s; the moisture permeability is 6000 to 10000 g/(m)2·24h)。
Detailed Description
In order to make the invention more comprehensible, preferred embodiments are described in detail below.
The raw materials used in the examples of the present invention were purchased from research platforms, except for the following specific descriptions. The eucommia ulmoides seed oil is a self-extracted medicine, and the dibutyltin dilaurate is purchased from Shanghai pharmaceutical group chemical reagent Limited.
Testing the hydroxyl value of the hyperbranched eucommia seed oil-based polyol by using a hydroxyl value titration analysis method; the water contact angle was measured by a contact angle measuring instrument (A801S, KINO Industry Co., U.S.A.); a universal material testing machine (SUN500, Italy Cardano ALCamp company) is adopted to carry out mechanical property test according to GB/T1040-; the films were tested for air permeability using an air permeability tester (model YG46E-I, Winzhou Bainn instruments Inc.) according to GB/T5453-1997; performing gas permeation test on the sample according to GB/T1038-2000 by using a differential pressure method gas permeameter (GBT-301, China Jinnan Seisan electronics science and technology Co., Ltd.); the moisture permeability was measured by a YG601H type computerized moisture permeability tester according to American Standard (ASTME96 BW-2000).
Example 1
A hyperbranched TPU hydrophilic film and a preparation method thereof are disclosed:
the raw materials used by the method comprise the following components in parts by weight:
(1) stirring the eucommia seed oil and formic acid for 1h at 40 ℃ by using sodium hydroxide as a catalyst, slowly adding hydrogen peroxide, and continuously stirring for 6h at 60 ℃. Then adding diethanolamine, stirring and standing, dissolving TPO with acetone and standing. Mixing the two solutions, and irradiating under 435W UV light for 6 min. The eucommia seed oil-based polyol with the hydroxyl value of 252mg KOH/g is obtained through reaction.
(2) And dehydrating the eucommia seed oil-based polyol at the temperature of 95 ℃ for 90 min. And cooling to 75 ℃, adding diisocyanate and dibutyltin dilaurate under the protection of nitrogen, and carrying out heat preservation reaction for 80 min. And (3) reducing the temperature of the system to 50 ℃, adding the micromolecule chain extender into the system, and keeping the temperature for reaction for 30 min.
(3) And adding the prepared TPU and DMF into a three-neck flask, and continuously stirring at 70 ℃ until the TPU and the DMF are completely dissolved to prepare a casting solution. Standing, sealing, removing bubbles, preparing a uniform liquid film with the thickness of 0.3mm on a clean glass plate, and immediately soaking the glass plate in a non-solvent for 24 hours; after the casting solution is subjected to phase separation and film formation, the prepared film is transferred from a glass plate to distilled water to be soaked and extracted to obtain excessive solvent and non-solvent.
The hydroxyl value of the hyperbranched eucommia seed oil-based polyol measured by the obtained eucommia seed oil-based thermoplastic polyurethane elastomer is 243mg KOH/g; the contact angle of the invention is 30.5 degrees through detection; the tensile strength is 35Mpa, and the elongation at break is 480%; the obtained TPU film has a film thickness of 0.35mm and H2Permeability of 3.2X 10-8mol·(m-2·s-1·Pa-1) (ii) a The gas permeation amount is 0.483 mm/s; under the conditions of 37 ℃ of temperature and 50% of relative humidity, the moisture permeability is 7800 g/(m)2·24h)。
Example 2
A hyperbranched TPU hydrophilic film and a preparation method thereof are disclosed:
the raw materials used by the method comprise the following components in parts by weight:
(1) stirring the eucommia seed oil and formic acid for 1h at 40 ℃ by using sodium hydroxide as a catalyst, slowly adding hydrogen peroxide, and continuously stirring for 6h at 60 ℃. Then adding diethanolamine, stirring and standing, dissolving TPO with acetone and standing. Mixing the two solutions, and irradiating under 435W UV light for 6 min. The eucommia seed oil-based polyol with the hydroxyl value of 293mg KOH/g is obtained through reaction.
(2) And dehydrating the eucommia seed oil-based polyol at the temperature of 95 ℃ for 90 min. And cooling to 75 ℃, adding diisocyanate and dibutyltin dilaurate under the protection of nitrogen, and carrying out heat preservation reaction for 80 min. And (3) reducing the temperature of the system to 50 ℃, adding the micromolecule chain extender into the system, and keeping the temperature for reaction for 30 min.
(3) And adding the prepared TPU and DMF into a three-neck flask, and continuously stirring at 70 ℃ until the TPU and the DMF are completely dissolved to prepare a casting solution. Standing, sealing, removing bubbles, preparing a uniform liquid film with the thickness of 0.3mm on a clean glass plate, and immediately soaking the glass plate in a non-solvent for 24 hours; after the casting solution is subjected to phase separation and film formation, the prepared film is transferred from a glass plate to distilled water to be soaked and extracted to obtain excessive solvent and non-solvent.
The hydroxyl value of the hyperbranched eucommia seed oil-based polyol measured by the obtained eucommia seed oil-based thermoplastic polyurethane elastomer is 260mg KOH/g; the contact angle of the invention is 27.2 degrees through detection; the tensile strength is 39.1Mpa, and the elongation at break is 593%; the obtained TPU film has a film thickness of 0.3mm and H2Permeability of 3.5X 10-8mol·(m-2·s-1·Pa-1) (ii) a The gas permeation amount is 0.598 mm/s; under the conditions of 37 ℃ of temperature and 50% of relative humidity, the moisture permeability is 9500 g/(m)2·24h)。
Example 3
A hyperbranched TPU hydrophilic film and a preparation method thereof are disclosed:
the raw materials used by the method comprise the following components in parts by weight:
(1) stirring the eucommia seed oil and formic acid for 1h at 40 ℃ by using sodium hydroxide as a catalyst, slowly adding hydrogen peroxide, and continuously stirring for 6h at 60 ℃. Then adding diethanolamine, stirring and standing, dissolving TPO with acetone and standing. Mixing the two solutions, and irradiating under 435W UV light for 6 min. The eucommia seed oil-based polyol with the hydroxyl value of 298mg KOH/g is obtained through reaction.
(2) And dehydrating the eucommia seed oil-based polyol at the temperature of 95 ℃ for 90 min. And cooling to 75 ℃, adding diisocyanate and dibutyltin dilaurate under the protection of nitrogen, and carrying out heat preservation reaction for 80 min. And (3) reducing the temperature of the system to 50 ℃, adding the micromolecule chain extender into the system, and keeping the temperature for reaction for 30 min.
(3) And adding the prepared TPU and DMF into a three-neck flask, and continuously stirring at 70 ℃ until the TPU and the DMF are completely dissolved to prepare a casting solution. Standing, sealing, removing bubbles, preparing a uniform liquid film with the thickness of 0.3mm on a clean glass plate, and immediately soaking the glass plate in a non-solvent for 24 hours; after the casting solution is subjected to phase separation and film formation, the prepared film is transferred from a glass plate to distilled water to be soaked and extracted to obtain excessive solvent and non-solvent.
The hydroxyl value of the hyperbranched eucommia seed oil-based polyol measured by the obtained eucommia seed oil-based thermoplastic polyurethane elastomer is 272mg KOH/g; the contact angle of the invention is 29.1 degrees through detection; tensile strength of 36MPa, elongation at break of 520%; the obtained TPU film is detected to have a film thickness of 0.38mm and H2Permeability of 3.1X 10-8mol·(m-2·s-1·Pa-1) (ii) a The gas permeation amount is 0.478 mm/s; the moisture permeability is 7500 g/(m) under the conditions that the temperature is 37 ℃ and the relative humidity is 50 percent2·24h)。
Claims (9)
1. The hyperbranched TPU hydrophilic film is characterized in that the raw materials comprise the following components in parts by weight:
the preparation method of the hyperbranched TPU hydrophilic film comprises the following steps:
step 1): under the action of a catalyst 1, mixing and stirring the eucommia seed oil and formic acid, slowly adding hydrogen peroxide, continuously stirring, then adding a hydroxyl compound, stirring and standing, uniformly mixing with a photoinitiator dissolved in acetone, and irradiating and reacting under UV light to obtain eucommia seed oil-based polyol;
step 2): dehydrating eucommia seed oil-based polyol, adding diisocyanate and a catalyst 2 under the protection of nitrogen for heat preservation reaction, adding a small-molecular chain extender into a system, and performing heat preservation reaction to obtain TPU;
step 3): continuously stirring TPU and a solvent at 60-85 ℃ until the TPU and the solvent are completely dissolved to prepare a casting solution, standing the casting solution, sealing and removing bubbles, preparing a liquid film on a clean glass plate, and immediately soaking the glass plate in a non-solvent for 24-48 h; after the film casting solution is subjected to phase separation to form a film, transferring the prepared film from a glass plate to distilled water for soaking and extracting excessive solvent and non-solvent.
2. The hyperbranched TPU hydrophilic film of claim 1 wherein the diisocyanate is at least one of isophorone diisocyanate, toluene diisocyanate, 4' -diphenylmethane diisocyanate, hexamethylene diisocyanate, and 1, 5-naphthalene diisocyanate.
3. The hyperbranched TPU hydrophilic film of claim 1, wherein the hydroxyl compound is at least one of diethanolamine and isopropanol.
4. The hyperbranched TPU hydrophilic film of claim 1, wherein the small molecule chain extender is one or both of 1, 4-butanediol and 1, 6-hexanediol.
5. The hyperbranched TPU hydrophilic film of claim 1, wherein the photoinitiator is one or both of 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide and a triarylsulfonium salt.
6. The hyperbranched TPU hydrophilic film of claim 1, wherein the catalyst 1 is at least one of sodium hydroxide and sodium carbonate; the catalyst 2 is at least one of dibutyltin dilaurate and stannous octoate.
7. The hyperbranched TPU hydrophilic film of claim 1, wherein the solvent is N, N-dimethylformamide; the non-solvent is one or more of water, methanol, ethanol and isopropanol.
8. The hyperbranched TPU hydrophilic film of claim 1, wherein step 1) is specifically: stirring the eucommia seed oil and formic acid for 1-2 hours at the temperature of 30-50 ℃ under the action of a catalyst 1, slowly adding hydrogen peroxide, continuously stirring for 6-8 hours at the temperature of 50-70 ℃, then adding a hydroxyl compound, stirring and standing, uniformly mixing with a photoinitiator dissolved in acetone, and irradiating and reacting for 3-8 minutes under the UV light of 400-475W to obtain the eucommia seed oil-based polyol with the hydroxyl value of 240-320 mgKOH/g.
9. The hyperbranched TPU hydrophilic film of claim 1, wherein step 2) is specifically: dehydrating the eucommia seed oil-based polyol at the temperature of 90-110 ℃ for 90-120 min, cooling to 65-85 ℃, adding diisocyanate and the catalyst 2 under the protection of nitrogen, reacting for 60-90 min under heat preservation, cooling to 40-60 ℃, adding the small molecular chain extender into the system, and reacting for 20-70 min under heat preservation.
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