CN112480361B - Preparation method of moisture-permeable thermoplastic polyurethane film - Google Patents
Preparation method of moisture-permeable thermoplastic polyurethane film Download PDFInfo
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- CN112480361B CN112480361B CN202011384274.7A CN202011384274A CN112480361B CN 112480361 B CN112480361 B CN 112480361B CN 202011384274 A CN202011384274 A CN 202011384274A CN 112480361 B CN112480361 B CN 112480361B
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- thermoplastic polyurethane
- film
- moisture
- diisocyanate
- polyurethane film
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- 239000004433 Thermoplastic polyurethane Substances 0.000 title claims abstract description 55
- 229920002803 thermoplastic polyurethane Polymers 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 229920006150 hyperbranched polyester Polymers 0.000 claims abstract description 26
- 229920005862 polyol Polymers 0.000 claims abstract description 26
- 150000003077 polyols Chemical class 0.000 claims abstract description 26
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 24
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000010096 film blowing Methods 0.000 claims abstract description 10
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 8
- 229940074391 gallic acid Drugs 0.000 claims abstract description 8
- 235000004515 gallic acid Nutrition 0.000 claims abstract description 8
- 239000004970 Chain extender Substances 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 29
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 15
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 13
- 239000000047 product Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 10
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 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 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000007664 blowing Methods 0.000 claims description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 6
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 5
- 239000006227 byproduct Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 229940113115 polyethylene glycol 200 Drugs 0.000 claims description 5
- 238000007493 shaping process Methods 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 4
- 229960004063 propylene glycol Drugs 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 claims description 2
- 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
- PISLZQACAJMAIO-UHFFFAOYSA-N 2,4-diethyl-6-methylbenzene-1,3-diamine Chemical compound CCC1=CC(C)=C(N)C(CC)=C1N PISLZQACAJMAIO-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- WUKNPIYSKBLCQI-UHFFFAOYSA-N CC(C=C1)=CC=C1C1=CC=C(C)C=C1.N=C=O.N=C=O Chemical compound CC(C=C1)=CC=C1C1=CC=C(C)C=C1.N=C=O.N=C=O WUKNPIYSKBLCQI-UHFFFAOYSA-N 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 claims description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-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
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229940057847 polyethylene glycol 600 Drugs 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 2
- 150000003384 small molecules Chemical group 0.000 claims description 2
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 claims description 2
- 229910000342 sodium bisulfate Inorganic materials 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 claims 1
- 230000035699 permeability Effects 0.000 abstract description 16
- 238000000071 blow moulding Methods 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 235000013305 food Nutrition 0.000 abstract description 2
- 238000004806 packaging method and process Methods 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 description 6
- 238000001514 detection method Methods 0.000 description 3
- 150000002009 diols Chemical class 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 235000003913 Coccoloba uvifera Nutrition 0.000 description 1
- 240000008976 Pterocarpus marsupium Species 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- VEIOBOXBGYWJIT-UHFFFAOYSA-N cyclohexane;methanol Chemical compound OC.OC.C1CCCCC1 VEIOBOXBGYWJIT-UHFFFAOYSA-N 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000010041 electrostatic spinning Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229940127554 medical product Drugs 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000004154 testing of material Methods 0.000 description 1
Classifications
-
- 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
- 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
-
- 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
- C08G18/4244—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups
- C08G18/4247—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids
- C08G18/4252—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids derived from polyols containing polyether groups and polycarboxylic 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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
-
- 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
- C08J2375/06—Polyurethanes from polyesters
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The invention belongs to the field of preparation of thermoplastic polyurethane films, and particularly relates to a preparation method of a moisture-permeable thermoplastic polyurethane film. Reacting citric acid with dihydric alcohol, adding gallic acid, and adding a catalyst to react to obtain hyperbranched polyester polyol with a large number of hydrophilic groups; the hyperbranched polyester polyol is reacted with diisocyanate and a micromolecular chain extender, and the thickness, the forming temperature and the relative temperature of the film are adjusted through a film blowing forming process to prepare the thermoplastic polyurethane film with a pore-free mode and good moisture permeability. The hyperbranched polyester polyol prepared by the invention has high branching degree, the tail end of the hyperbranched polyester polyol has a large number of hydrophilic groups, and a more economic blow molding process is adopted, so that the synthesis process is simple. The thermoplastic polyurethane film prepared by the process has good hydrophilicity, mechanical property and moisture permeability, and has application value in the fields of medical supplies, clothes, home furnishing, food packaging and the like.
Description
The technical field is as follows:
the invention belongs to the field of preparation of thermoplastic polyurethane films, and particularly relates to a preparation method of a moisture-permeable thermoplastic polyurethane film.
Background art:
thermoplastic polyurethane film (TPU film for short) is an elastic block copolymer which is mainly made of diisocyanate or polyester/polyether diol and consists of a flexible soft segment area and a rigid functional group hard segment area. The special chemical structure not only endows the material with excellent mechanical property and wear resistance, but also has the advantages of good toughness, oil resistance, corrosion resistance and the like, is a mature environment-friendly material, and is widely applied to the fields of medical products, clothes, home decoration, building materials, food packaging and the like. Although the TPU film has good waterproof performance, the TPU film usually has poor permeability to oxygen, water vapor and other small molecular substances, in order to improve the hydrophilicity and moisture permeability of the TPU film, researches are mostly carried out by introducing hydrophilic polyester/polyether diol and chemical bonding hydrophilic functional groups singly or preparing microporous or non-porous TPU films by physical techniques such as electrostatic spinning and air spinning, and the like. Therefore, by improving the chemical structure of the TPU, the TPU film has more hydrophilic groups to improve the hydrophilic moisture permeability, and a certain forming process is adopted to prepare the TPU film with no holes, good moisture permeability and uniform thickness, so that the comprehensive performance of the TPU film can be improved and the application field of the TPU film can be enlarged.
With the improvement of living standard of people, certain requirements are required on the waterproofness and the air permeability of materials in the industries of clothes, outdoor articles, medical supplies and the like. The hyperbranched polyester polyol has the characteristics of high branching, a large number of terminal functional groups, ordered structure, monodispersity and the like, and meanwhile, the hyperbranched polyester polyol is simple in synthesis process and has lower viscosity and good fluidity compared with the common polyester polyol. The hyperbranched polyester polyol tail segment has a large number of hydrophilic groups, and is used as a raw material to prepare a TPU film, so that the hydrophilic moisture permeability of the film can be improved to a great extent, and the film is processed into a waterproof and high-moisture-permeability pore-free film through a film coating, film blowing or rolling mode, and the like, so that the film can be applied to various industries.
Therefore, the invention discloses a hydrophilic TPU film prepared from hyperbranched polyester polyol with a large number of hydrophilic groups, and the TPU film with a pore-free shape and good moisture permeability is prepared by a certain forming technology, so that the invention has a good application prospect.
The invention content is as follows:
the invention aims at the problems and provides a preparation method of a moisture-permeable thermoplastic polyurethane film.
In order to achieve the purpose, the invention adopts the following technical scheme that the preparation method comprises the following specific steps,
1. preparation of hyperbranched polyester polyols
Putting 10-30 parts by weight of citric acid and 5-40 parts by weight of dihydric alcohol into a three-neck round-bottom flask, heating to 100-150 ℃, introducing nitrogen, and stirring for 1-2 hours; adding 30-100 parts by weight of gallic acid, stirring at 120-150 ℃ for 0.5-2 h, adding 0.2-1 part by weight of catalyst, continuing stirring for 0.5-2 h, vacuumizing the reaction system for about 5min at intervals of 0.5h to remove small molecular byproducts, and stopping the reaction until the weight of the reaction system is not obviously changed to obtain hyperbranched polyester polyol;
2. preparation of hydrophilic thermoplastic polyurethanes
Respectively removing water for 1-2 hours at 50-70 ℃ in vacuum by using 30-60 parts by weight of diisocyanate and 15-30 parts by weight of micromolecular chain extender; adding 30-60 parts by weight of the hyperbranched polyester polyol prepared in the step 1 into a three-neck flask provided with a stirring device, heating to 100-130 ℃, vacuumizing and dehydrating for 0.5-2 h, cooling to 80-100 ℃, adding molten and dehydrated diisocyanate, stirring for 1-2 h, continuously adding the dehydrated micromolecule chain extender, and stirring for 1-2 h at 70-100 ℃ to obtain the hydrophilic thermoplastic polyurethane;
3. preparation of moisture-permeable thermoplastic polyurethane film
And (3) quickly pouring the product obtained in the step (2) into a film blowing machine for melt blending, setting the blowing width, the blowing thickness and the three-section temperature of a machine head of the film blowing machine set according to requirements for film blowing, finally, cooling and shaping the film by using a cooling machine, and drying the obtained thermoplastic polyurethane film at the temperature of 20-45 ℃ for 0.2-2.0 h to obtain the moisture-permeable thermoplastic polyurethane film.
Preferably, the diol in step 1 is one or more of ethylene glycol, propylene glycol, polytetrahydrofuran glycol, polyethylene glycol 200, polyethylene glycol 600 and polypropylene glycol.
Preferably, the catalyst in step 1 is one or more of sodium bisulfate, p-toluenesulfonic acid, concentrated sulfuric acid and concentrated hydrochloric acid.
Preferably, the diisocyanate in the step 2 is one or more of diphenylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, 1, 5-naphthalene diisocyanate, p-phenylene diisocyanate, and dimethyl biphenyl diisocyanate;
preferably, the small molecule chain extender in step 2 is one or more of ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 6-hexanediol, cyclohexane dimethanol, diethylene glycol, glycerol, ethylenediamine, triethanolamine, triisopropanolamine, diethyl toluene diamine, and N-methyl diethanolamine;
preferably, in the step 3, the width of the blown film is 150 cm-160 cm, the thickness of the blown film is 0.2 mm-0.5 mm, and the temperature interval of the three sections of the head of the film blowing unit is 155-175 ℃.
The invention has the beneficial effects that:
1. the invention introduces two biological raw materials of citric acid and gallic acid to prepare the hyperbranched polyester polyol, and the preparation process has no use of organic solvent and simple operation. The gallic acid and citric acid are sustainable biological resources and have low cost, and the molecular structure has a terminal polyhydroxy and carboxyl branched structure. The prepared hyperbranched polyester polyol is environment-friendly hyperbranched polyester polyol, has high branching degree, has a large number of hydrophilic groups at the tail end, and has good hydrophilicity.
2. The invention provides a hyperbranched polyester polyol synthesized moisture permeable thermoplastic polyurethane film and a preparation method thereof, and the hyperbranched polyester polyol synthesized moisture permeable thermoplastic polyurethane film has the advantages of simple production process and low cost and is suitable for industrial production. Compared with a microporous film, the microporous film has the advantages of better wind resistance and water resistance, microorganism isolation, no influence of dust and the like. Compared with the casting and extrusion film forming processes, the blow molding process is more economical, the blow-up ratio is easy to control, and the controllable range of the film thickness is large. Hydrophilic films are sensitive to temperature and humidity, and their moisture permeability depends on the thickness of the film and its chemical structure and degree of crosslinking. The hyperbranched polyester polyol is introduced to change the chemical structure of the TPU, and the thickness and the forming temperature of the film are adjusted to prepare the TPU film with uniform thickness, no pore and good moisture permeability.
The specific implementation mode is as follows:
the raw materials used in the examples were purchased from the research platform.
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 moisture permeability was measured by a YG601H type computerized moisture permeability tester according to American Standard (ASTME96 BW-2000).
Example 1
1kg of citric acid and 2.5kg of polyethylene glycol 200 by weight are placed in a three-necked round-bottomed flask equipped with a nitrogen inlet, a thermometer and a mechanical stirrer, heated to 140 ℃, introduced with nitrogen and stirred for 2 hours; adding 3kg of gallic acid, stirring at 120 ℃ for 2h, adding 0.05kg of p-toluenesulfonic acid, continuously stirring for 1.5h, vacuumizing the reaction system for about 5min at intervals of 0.5h to remove small molecular by-products, and stopping the reaction until the weight of the reaction system is not obviously changed to obtain the hyperbranched polyester polyol;
firstly, respectively removing water in vacuum for 1h at 60 ℃ by 3kg of isophorone diisocyanate and 1.5kg of 1, 4-butanediol; adding 3kg of prepared hyperbranched polyester polyol into a three-neck flask provided with a stirring device, heating to 120 ℃, vacuumizing and dehydrating for 1.5h, cooling to 80 ℃, adding molten and dehydrated isophorone diisocyanate, stirring for 1h, continuously adding dehydrated 1, 4-butanediol, and stirring for 1h at 80 ℃ to obtain the hydrophilic thermoplastic polyurethane;
and (2) quickly pouring the product into a die head of a blow molding machine, processing the product by using the blow molding machine (the blowing ratio is set to be 2.5, the traction speed is set to be 30m/min), blowing the product with the width of 155cm, the temperature of three sections of a machine head is 155 ℃, 160 ℃ and 165 ℃, adjusting the thickness of the film by using the die head to be 0.2mm, finally cooling and shaping the film by using a cooling machine, and drying the obtained thermoplastic polyurethane film at the temperature of 45 ℃ for 1.0h to obtain the moisture-permeable thermoplastic polyurethane film.
The water contact angle of the moisture-permeable thermoplastic polyurethane film is 31.5 degrees through detection; tensile strength of 37.2Mpa, elongation at break of 489%; the moisture permeability is 11046g/(m2 & 24h) under the conditions that the temperature is 35 ℃ and the relative humidity is 50 percent.
Example 2
Placing 1.5kg of citric acid and 3kg of polyethylene glycol 200 in parts by weight in a three-necked round-bottomed flask equipped with a nitrogen inlet, a thermometer and a mechanical stirrer, heating to 140 ℃, introducing nitrogen, and stirring for 2 hours; adding 3kg of gallic acid, stirring at 120 ℃ for 2h, adding 0.05kg of p-toluenesulfonic acid, continuously stirring for 1.5h, vacuumizing the reaction system for about 5min at intervals of 0.5h to remove small molecular by-products, and stopping the reaction until the weight of the reaction system is not obviously changed to obtain the hyperbranched polyester polyol;
firstly, respectively removing water in vacuum for 1h at 60 ℃ by 3kg of isophorone diisocyanate and 1.5kg of 1, 4-butanediol; adding 3kg of prepared hyperbranched polyester polyol into a three-neck flask provided with a stirring device, heating to 120 ℃, vacuumizing and dehydrating for 1.5h, cooling to 80 ℃, adding molten and dehydrated isophorone diisocyanate, stirring for 1h, continuously adding dehydrated 1, 4-butanediol, and stirring for 1h at 80 ℃ to obtain the hydrophilic thermoplastic polyurethane;
quickly pouring the product into a die head of a blow molding machine, processing the product by using the blow molding machine (the blow-up ratio is set to be 2.5, the traction speed is set to be 32m/min), blowing the product with the width of 153cm, adjusting the thickness of the film by using the die head to be 0.25mm, finally cooling and shaping the film by using a cooling machine, and drying the obtained thermoplastic polyurethane film for 1.5 hours at the temperature of 35 ℃ to obtain the moisture-permeable thermoplastic polyurethane film;
the water contact angle of the moisture-permeable thermoplastic polyurethane film is 33.8 degrees through detection; the tensile strength is 34.4Mpa, the elongation at break is 463%; under the conditions that the temperature is 35 ℃ and the relative humidity is 50%, the moisture permeability is 10923g/(m2 & 24 h).
Example 3
Placing 1.5kg of citric acid and 3.5kg of polyethylene glycol 200 into a three-necked round bottom flask equipped with a nitrogen inlet, a thermometer and a mechanical stirrer, heating to 140 ℃, introducing nitrogen, and stirring for 2 hours; adding 3kg of gallic acid, stirring at 120 ℃ for 2h, adding 0.05kg of p-toluenesulfonic acid, continuously stirring for 1.5h, vacuumizing the reaction system for about 5min at intervals of 0.5h to remove small molecular by-products, and stopping the reaction until the weight of the reaction system is not obviously changed to obtain the hyperbranched polyester polyol;
firstly, respectively removing water in vacuum for 1h at 60 ℃ by 3kg of isophorone diisocyanate and 1.5kg of 1, 4-butanediol; adding 3kg of prepared hyperbranched polyester polyol into a three-neck flask provided with a stirring device, heating to 120 ℃, vacuumizing and dehydrating for 1.5h, cooling to 80 ℃, adding molten and dehydrated isophorone diisocyanate, stirring for 1h, continuously adding dehydrated 1, 4-butanediol, and stirring for 1h at 80 ℃ to obtain the hydrophilic thermoplastic polyurethane;
and (2) quickly pouring the product into a die head of a blow molding machine, processing the product by using the blow molding machine (the blowing-up ratio is set to be 2.5, the traction speed is set to be 30m/min), blowing the product with the width of 158cm, the temperature of three sections of the machine head is 165 ℃, 170 ℃ and 175 ℃, adjusting the thickness of the film by using the die head to be 0.3mm, finally cooling and shaping the film by using a cooling machine, and drying the obtained thermoplastic polyurethane film at the temperature of 30 ℃ for 2.0h to obtain the moisture-permeable thermoplastic polyurethane film.
The water contact angle of the moisture-permeable thermoplastic polyurethane film is 35.9 degrees through detection; the tensile strength is 31.7Mpa, and the elongation at break is 455%; the moisture permeability is 10558g/(m 2h 24h) under the conditions that the temperature is 35 ℃ and the relative humidity is 50%.
The above description is only a basic description of the present invention, and any equivalent changes made according to the technical solution of the present invention should fall within the protection scope of the present invention.
Claims (6)
1. A preparation method of a moisture permeable thermoplastic polyurethane film is characterized by comprising the following specific preparation steps,
(1) preparation of hyperbranched polyester polyols
Putting 10-30 parts by weight of citric acid and 5-40 parts by weight of dihydric alcohol into a three-neck round-bottom flask, heating to 100-150 ℃, introducing nitrogen, and stirring for 1-2 hours; adding 30-100 parts by weight of gallic acid, stirring at 120-150 ℃ for 0.5-2 h, adding 0.2-1 part by weight of catalyst, continuing stirring for 0.5-2 h, vacuumizing the reaction system for about 5min at intervals of 0.5h to remove small molecular byproducts, and stopping the reaction until the weight of the reaction system is not obviously changed to obtain hyperbranched polyester polyol;
(2) preparation of hydrophilic thermoplastic polyurethanes
Respectively removing water for 1-2 hours at 50-70 ℃ in vacuum by using 30-60 parts by weight of diisocyanate and 15-30 parts by weight of micromolecular chain extender; adding 30-60 parts by weight of the hyperbranched polyester polyol prepared in the step 1) into a three-neck flask provided with a stirring device, heating to 100-130 ℃, vacuumizing and dehydrating for 0.5-2 h, cooling to 80-100 ℃, adding molten and dehydrated diisocyanate, stirring for 1-2 h, continuously adding the dehydrated micromolecule chain extender, and stirring for 1-2 h at 70-100 ℃ to obtain the hydrophilic thermoplastic polyurethane;
(3) preparation of moisture-permeable thermoplastic polyurethane film
And (3) quickly pouring the product obtained in the step 2) into a film blowing machine for melt blending, setting the blowing width and thickness and the three-section temperature of a machine head of the film blowing machine set according to requirements for film blowing, finally, cooling and shaping the film by using a cooling machine, and drying the obtained thermoplastic polyurethane film at the temperature of 20-45 ℃ for 0.2-2.0 h to obtain the moisture-permeable thermoplastic polyurethane film.
2. The method for preparing the moisture-permeable thermoplastic polyurethane film according to claim 1, wherein the glycol in the step 1) is one or more of ethylene glycol, propylene glycol, polytetrahydrofuran glycol, polyethylene glycol 200, polyethylene glycol 600 and polypropylene glycol.
3. The method for preparing the moisture-permeable thermoplastic polyurethane film according to claim 1, wherein the catalyst in the step 1) is one or more of sodium bisulfate, p-toluenesulfonic acid, concentrated sulfuric acid and concentrated hydrochloric acid.
4. The method for preparing the moisture-permeable thermoplastic polyurethane film according to claim 1, wherein the diisocyanate in the step 2) is one or more of diphenylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, 1, 5-naphthalene diisocyanate, p-phenylene diisocyanate, and dimethylbiphenyl diisocyanate.
5. The method for preparing the moisture-permeable thermoplastic polyurethane film according to claim 1, wherein the small-molecule chain extender in the step 2) is one or more selected from ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 6-hexanediol, cyclohexanedimethanol, diethylene glycol, glycerol, ethylenediamine, triethanolamine, triisopropanolamine, diethyltoluenediamine, and N-methyldiethanolamine.
6. The method for preparing the moisture-permeable thermoplastic polyurethane film according to claim 1, wherein the blown width in the step 3) is 150cm to 160cm, the blown film thickness is 0.2mm to 0.5mm, and the temperature ranges of the three sections of the head of the film blowing unit are 155 ℃ to 175 ℃.
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