CN113045725A - Preparation method of antifogging TPU material and preparation method of film - Google Patents
Preparation method of antifogging TPU material and preparation method of film Download PDFInfo
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- CN113045725A CN113045725A CN202110379423.9A CN202110379423A CN113045725A CN 113045725 A CN113045725 A CN 113045725A CN 202110379423 A CN202110379423 A CN 202110379423A CN 113045725 A CN113045725 A CN 113045725A
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- 239000000463 material Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 45
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 45
- 239000002994 raw material Substances 0.000 claims abstract description 35
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims abstract description 34
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 20
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims abstract description 19
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims abstract description 19
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 19
- 230000008569 process Effects 0.000 claims abstract description 18
- 239000000314 lubricant Substances 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 17
- 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 abstract description 14
- 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 abstract description 14
- 238000001816 cooling Methods 0.000 claims abstract description 12
- 239000005058 Isophorone diisocyanate Substances 0.000 claims abstract description 8
- 208000005156 Dehydration Diseases 0.000 claims abstract description 7
- 230000018044 dehydration Effects 0.000 claims abstract description 7
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 7
- 238000001125 extrusion Methods 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000004970 Chain extender Substances 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- 229920006267 polyester film Polymers 0.000 claims description 9
- 238000005266 casting Methods 0.000 claims description 8
- 239000002131 composite material Substances 0.000 claims description 8
- 238000005507 spraying Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 239000004743 Polypropylene Substances 0.000 claims description 5
- 238000011049 filling Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- -1 polypropylene Polymers 0.000 claims description 5
- 229920001155 polypropylene Polymers 0.000 claims description 5
- ZMZQVAUJTDKQGE-UHFFFAOYSA-N 2-ethylhydracrylic acid Chemical compound CCC(CO)C(O)=O ZMZQVAUJTDKQGE-UHFFFAOYSA-N 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000007493 shaping process Methods 0.000 claims description 4
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 3
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 3
- 235000021355 Stearic acid Nutrition 0.000 claims description 3
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 3
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000012188 paraffin wax Substances 0.000 claims description 3
- 239000008117 stearic acid Substances 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 13
- 239000002245 particle Substances 0.000 abstract description 6
- 230000000704 physical effect Effects 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000002834 transmittance Methods 0.000 description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 230000032683 aging Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 1
- 241001274961 Rubus repens Species 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000009189 diving Effects 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000013611 frozen food Nutrition 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002523 polyethylene Glycol 1000 Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000007740 vapor deposition 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
- C08G18/28—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
-
- 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
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/2815—Monohydroxy compounds
- C08G18/283—Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds
-
- 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
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- 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
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
-
- 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
- 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
- C08J2375/08—Polyurethanes from polyethers
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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)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
A preparation method of an antifogging TPU material comprises the following steps: step 1, preparing raw materials according to the following proportions: 30-55% of polyethylene glycol, 10-20% of trimethylolpropane polyethylene glycol monomethyl ether, 3-20% of 1, 4-butanediol, 1-5% of dimethylolbutyric acid, 1-5% of polyethylene oxide, 15-45% of isophorone diisocyanate, and 1-3% of antioxidant, lubricant and stannous octoate in total; step 2, carrying out negative pressure dehydration treatment on 1, 4-butanediol, dimethylolbutyric acid and polyethylene oxide; step 3, stirring and mixing the raw materials at the temperature of 90 ℃; step 4, baking the mixed raw materials, and cooling to normal temperature; and 5, crushing the mixed raw materials, and performing an extrusion process to form the antifogging TPU material. The anti-fog TPU particles prepared by the method have high production efficiency and low cost, and can ensure the physical properties such as tearing strength, tension and the like on the premise of ensuring the hydrophilic property and realizing the anti-fog effect.
Description
Technical Field
The invention relates to a preparation method of a TPU material, in particular to a preparation method of an antifogging TPU material and a preparation method of a film.
Background
Polyurethane (TPU) has excellent characteristics of high tension, high tensile force, toughness and aging resistance, and is a mature environment-friendly material. At present, TPU is widely applied to the aspects of medical sanitation, electronic and electric appliances, industry, sports and the like, has the characteristics of high strength, good toughness, wear resistance, cold resistance, oil resistance, water resistance, aging resistance, weather resistance and the like which cannot be compared with other plastic materials, and simultaneously has a plurality of excellent functions of high waterproofness and moisture permeability, wind resistance, cold resistance, antibiosis, mildew resistance, warm keeping, ultraviolet resistance, energy release and the like.
Since the innovation, the demand for TPU products has dramatically increased in quality requirements in addition to the enormous increase in consumption, such as the antifogging effect required by many products: the antifogging of the frozen food package is to facilitate the consumers to clearly see the states of fruits and meat of the food; the antifogging of the agricultural film is to see through the change of crops in various environments with low temperature and high temperature; the antifogging of the diving goggles is to ensure that a colorful world under water can be still seen under the long-term use; the anti-fog of the street lamp aims to illuminate the road surface without generating dew drops in severe environment and reduce accidents caused by insufficient lighting of the street lamp in rainy days and at high temperature or low temperature.
The products on the market at present are mainly prepared by compounding titanium dioxide or other inorganic substances and then processing the titanium dioxide or other inorganic substances for 24 to 48 hours by a vapor deposition method under the condition of high temperature energy consumption, so that a hydrophilic film layer is formed on a polyester film, and although the hydrophilic film layer has an excellent anti-fog effect, the yield is low and the cost is extremely high.
The other type of products are compounded by raw materials composed of hydrophilic monomers mainly comprising surfactants, and although the initial effect is good, most of the surfactants are monomers or oligomers, so that the surfactants do not have the required physical properties and are easy to precipitate and lose efficacy.
Disclosure of Invention
The technical scheme of the invention is to solve the above problems and provide a preparation method of an anti-fog TPU material, which comprises the following steps:
step 1, preparing raw materials according to the following proportions: 30-55% of polyethylene glycol, 10-20% of trimethylolpropane polyethylene glycol monomethyl ether, 3-20% of 1, 4-butanediol, 1-5% of dimethylolbutyric acid, 1-5% of polyethylene oxide, 15-45% of isophorone diisocyanate, and 1-3% of antioxidant, lubricant and stannous octoate in total;
step 2, carrying out negative pressure dehydration treatment on 1, 4-butanediol, dimethylolbutyric acid and polyethylene oxide until the water content is below 100 PPM;
step 3, stirring and mixing the raw materials at the temperature of 90 ℃;
step 4, baking the mixed raw materials, and cooling to normal temperature;
and 5, crushing the mixed raw materials, and performing an extrusion process to form the antifogging TPU material.
Further, in step 1, the hydroxyl value of polyethylene glycol is 37 to 120, the hydroxyl value of trimethylolpropane polyethylene glycol monomethyl ether is 112, and the hydroxyl value of polyethylene oxide is 540 to 580.
Further, in the step 1, the ratio of the total ratio of the composite chain extender of hydroxymethylbutyric acid and polyethylene oxide to the ratio of the chain extender of 1, 4-butanediol is 4: 6.
further, in step 1, the antioxidant is one or more of antioxidant BHT, antioxidant 1010, antioxidant 1076 and antioxidant 168.
Further, in step 1, the lubricant is one or a mixture of paraffin and stearic acid.
Further, in step 2, the degree of vacuum in the negative pressure water removal process is less than 2 Torr.
Further, step 3 specifically includes:
step 3.1, inputting nitrogen into the stirring device, maintaining the air pressure of 0.1MPa, heating to 90 ℃, pouring polyethylene glycol, trimethylolpropane polyethylene glycol monomethyl ether, isophorone diisocyanate, an antioxidant, a lubricant and stannous octoate, stirring, and reacting for 2 hours;
step 3.2, cooling to 70 ℃, pouring 1, 4-butanediol, dimethylolbutyric acid and polyethylene oxide, stirring, and reacting for 1-2 hours;
and 3.3, filling the mixture into a polypropylene disk container.
Further, step 4 specifically includes:
step 4.1, placing the mixed raw materials into an oven, heating to 90 ℃, vacuumizing by using a vacuum pump, and maintaining the vacuum degree of 650mmHg for 5 hours;
step 4.2, raising the temperature to 105 ℃, keeping the vacuum degree at 650mmHg, and maintaining for 2 hours;
step 4.3, changing the vacuum degree to 750mmHg, heating to 140 ℃, and maintaining for 3 hours;
and 4.4, closing the oven, and standing the mixed raw materials.
The invention also provides a preparation method of the antifogging TPU film, which comprises the following steps:
step 1, carrying out a casting process on the antifogging TPU material of claim 1 through a casting machine;
step 2, spraying the molten TPU material on release paper or a polyester film through a film spraying process;
and 3, cooling, shaping and coiling to obtain the antifogging TPU film.
The invention also provides a preparation method of the antifogging TPU film, which comprises the following steps:
step 1, carrying out a dissolving process on the antifogging TPU material of claim 1 through a solvent;
step 2, coating the dissolved TPU material on release paper or a polyester film through a coating process;
and 3, drying and coiling to obtain the antifogging TPU film.
After the technical scheme is adopted, the invention has the effects that: the anti-fog TPU particles prepared by the method have high production efficiency and low cost, and can ensure the physical properties such as tearing strength, tension and the like on the premise of ensuring the hydrophilic property and realizing the anti-fog effect.
Detailed Description
The technical solution of the present invention is further described by the following examples:
the invention provides a preparation method of an antifogging TPU material, which comprises the following steps:
step 1, preparing raw materials according to the following proportions: 30-55% of polyethylene glycol (PEG), 10-20% of trimethylolpropane polyethylene glycol monomethyl ether (N120), 3-20% of 1, 4-Butanediol (BDO), 1-5% of dimethylolbutyric acid (DMBA), 1-5% of polyethylene oxide (PEO), 15-45% of isophorone diisocyanate (IPDI), and 1-3% of antioxidant, lubricant and stannous octoate in total;
step 2, carrying out negative pressure dehydration treatment on the 1, 4-butanediol, the dimethylolbutyric acid and the polyethylene oxide by using a negative pressure dehydration device until the water content is below 100 PPM;
step 3, stirring and mixing the raw materials at the temperature of 90 ℃ by a stirring device, and filling the mixture into a polypropylene disk container;
step 4, placing the mixed raw materials into an oven for baking, taking out and cooling to normal temperature;
and 5, crushing the mixed raw materials by using a crusher, and performing an extrusion process by using a single-screw extruder to form the antifogging TPU material (usually a granular material).
Wherein polyethylene glycol and trimethylolpropane polyethylene glycol monomethyl ether are used as dihydric alcohols; 1, 4-butanediol is used as a chain extender, and dimethylol butyric acid and polyethylene oxide are used as composite chain extenders; isophorone diisocyanate is used for forming a main structure and a hydrogen bond of polyurethane; antioxidants are used to prevent thermal oxidative degradation; the lubricant is used for lubricating; stannous octoate was used as the catalyst.
Firstly, the raw materials of the invention adopt dihydric alcohol with excellent hydrophilicity: polyethylene glycol, wherein the hydrophilic group of the polyethylene glycol can reduce the water drop angle so as to achieve an anti-fog effect; the chain extender adopts a composite chain extender with excellent hydrophilicity: the hydrophilic performance of the TPU material formed by the polyethylene oxide and the dimethylolbutyric acid is enough to be applied to various fields needing antifogging work, and the antifogging effect of the TPU material is increased along with the increase of the dosage of the two composite chain extenders relative to the dosage of the 1, 4-butanediol (namely the proportion of the dosage of the composite chain extenders in the total dosage of the chain extenders is increased). Secondly, the trimethylolpropane polyethylene glycol monomethyl ether contains a macromolecular hydrophilic group on a side chain, so that the TPU material has a long-acting hydrophilic effect.
More importantly, in the invention, as the chain extenders are subjected to water removal treatment, the influence of urea bonds generated by isocyanate and water on the antifogging effect can be avoided in the reaction polymerization process.
The hydrophilic groups of the main chain of the antifogging TPU material are arranged as follows:
PEG1000/N120-IPDI-DMBA-IPDI-PEG200-IPDI-BDO-…
the corresponding molecular weights are as follows:
(1000)-(222)-(148)-(222)-(200)-(222)-(90)-…
therefore, the anti-fog TPU particles prepared by the method have high production efficiency and low cost, and can ensure the physical properties such as tear strength, tension and the like on the premise of ensuring the hydrophilic property and realizing the anti-fog effect.
Specifically, in the step 1, the hydroxyl value of the polyethylene glycol is 37-120, the hydroxyl value of the trimethylolpropane polyethylene glycol monomethyl ether is 112, and the hydroxyl value of the polyethylene oxide is 540-580.
Specifically, in step 1, the ratio of the total ratio of the composite chain extender hydroxymethylbutyric acid and polyethylene oxide to the ratio of the chain extender 1, 4-butanediol is 4: 6. when the total proportion of the composite chain extender hydroxymethylbutyric acid and polyethylene oxide is not more than 40 percent of the total using amount of the chain extender, the water contact angle of the prepared antifogging TPU film is about 10 degrees, and the tear strength of the antifogging TPU film can be maintained at 80kg/cm2The above.
Specifically, in step 1, the antioxidant is one or more of antioxidant BHT, antioxidant 1010, antioxidant 1076, and antioxidant 168.
Specifically, in step 1, the lubricant is one or a mixture of paraffin and stearic acid.
Specifically, in step 2, the degree of vacuum of the negative pressure water removal process is less than 2 Torr. The efficiency and effect of removing water in Australia can be achieved under the vacuum degree.
More specifically, step 3 specifically includes:
step 3.1, inputting nitrogen into the stirring device, maintaining the air pressure of 0.1MPa, heating to 90 ℃, pouring polyethylene glycol, trimethylolpropane polyethylene glycol monomethyl ether, isophorone diisocyanate, an antioxidant, a lubricant and stannous octoate, stirring, and reacting for 2 hours;
step 3.2, cooling to 70 ℃, pouring 1, 4-butanediol, dimethylolbutyric acid and polyethylene oxide, stirring, and reacting for 1-2 hours (until the viscosity reaches above 20000 CPS);
and 3.3, filling the mixture into a polypropylene disk container.
Wherein, the input of nitrogen can block the moisture in the air; the viscosity of the product reaches above 20000CPS, which is a necessary condition for ensuring the smooth formation of the finished product.
Specifically, step 4 specifically includes:
step 4.1, placing the mixed raw materials into an oven, heating to 90 ℃, vacuumizing by using a vacuum pump, and maintaining the vacuum degree of 650mmHg for 5 hours;
step 4.2, raising the temperature to 105 ℃, keeping the vacuum degree at 650mmHg, and maintaining for 2 hours;
step 4.3, changing the vacuum degree to 750mmHg, heating to 140 ℃, and maintaining for 3 hours;
and 4.4, closing the oven, and standing the mixed raw materials.
In the step 4, the raw material is baked in three stages and vacuumized (i.e. further water removal), so that slow three-stage water removal can be realized, the water removal effect is improved, and the raw material is prevented from being pumped away in the vacuumizing process.
The invention also provides a preparation method of the antifogging TPU film, which comprises the following steps:
step 1, carrying out a casting process on the antifogging TPU material through a casting machine;
step 2, spraying the molten TPU material on release paper or a polyester film through a film spraying process;
and 3, cooling, shaping and coiling to obtain the antifogging TPU film.
The invention also provides another preparation method of the antifogging TPU film, which comprises the following steps:
step 1, carrying out a dissolving process on the antifogging TPU material through a solvent;
step 2, coating the dissolved TPU material on release paper or a polyester film through a coating process;
and 3, drying and coiling to obtain the antifogging TPU film.
Specifically, in step 1, the solvent is a MEK solvent or DMAC solvent.
[ example 1 ]
In this embodiment, the preparation method of the anti-fog TPU material includes:
step 1, preparing raw materials according to the following weight: 4.3kg of polyethylene glycol (PEG), 1.06kg of trimethylolpropane polyethylene glycol monomethyl ether (N120), 0.91kg of 1, 4-Butanediol (BDO), 0.11kg of dimethylolbutyric acid (DMBA), 0.11kg of polyethylene oxide (PEO), 3.54kg of isophorone diisocyanate (IPDI), 0.02kg of antioxidant, 0.02kg of lubricant and 0.002kg of stannous octoate;
step 2, carrying out negative pressure dehydration treatment on the 1, 4-butanediol, the dimethylolbutyric acid and the polyethylene oxide by using a negative pressure dehydration device until the water content is below 100 PPM;
step 3.1, inputting nitrogen into the stirring device, maintaining the air pressure of 0.1MPa, heating to 90 ℃, pouring polyethylene glycol, trimethylolpropane polyethylene glycol monomethyl ether, isophorone diisocyanate, an antioxidant, a lubricant and stannous octoate, stirring, and reacting for 2 hours;
step 3.2, cooling to 70 ℃, pouring 1, 4-butanediol, dimethylolbutyric acid and polyethylene oxide, stirring, and reacting for 1-2 hours (until the viscosity reaches above 20000 CPS);
step 3.3, filling the mixture into a polypropylene disk container;
step 4.1, placing the mixed raw materials into an oven, heating to 90 ℃, vacuumizing by using a vacuum pump, and maintaining the vacuum degree of 650mmHg for 5 hours;
step 4.2, raising the temperature to 105 ℃, keeping the vacuum degree at 650mmHg, and maintaining for 2 hours;
step 4.3, changing the vacuum degree to 750mmHg, heating to 140 ℃, and maintaining for 3 hours;
step 4.4, closing the oven, and standing the mixed raw materials;
and 5, crushing the mixed raw materials by using a crusher, and performing an extrusion process by using a single-screw extruder to form the antifogging TPU particle material.
In this embodiment, the preparation method of the anti-fog TPU film includes:
step 1, carrying out a casting process on the anti-fog TPU particles through a casting machine;
step 2, spraying the molten TPU material on release paper or a polyester film through a film spraying process;
and 3, cooling, shaping and coiling to obtain the antifogging TPU film with the thickness of 0.3 mm.
[ example 2 ]
The preparation methods of the antifogging TPU material and the antifogging TPU film of this embodiment are similar to those of embodiment 1, and the same parts are not described herein again, except that:
in step 1, the raw materials are prepared according to the following weight: 3.62kg of polyethylene glycol (PEG), 0.9kg of trimethylolpropane polyethylene glycol monomethyl ether (N120), 1.16kg of 1, 4-Butanediol (BDO), 0.14kg of dimethylolbutyric acid (DMBA), 0.14kg of polyethylene oxide (PEO), 4kg of isophorone diisocyanate (IPDI), 0.02kg of antioxidant, 0.02kg of lubricant and 0.002kg of stannous octoate.
[ example 3 ]
The preparation methods of the antifogging TPU material and the antifogging TPU film of this embodiment are similar to those of embodiment 1, and the same parts are not described herein again, except that:
in step 1, the raw materials are prepared according to the following weight: 3.15kg of polyethylene glycol (PEG), 0.78kg of trimethylolpropane polyethylene glycol monomethyl ether (N120), 1.347kg of 1, 4-Butanediol (BDO), 0.16kg of dimethylolbutyric acid (DMBA), 0.16kg of polyethylene oxide (PEO), 4.38kg of isophorone diisocyanate (IPDI), 0.02kg of antioxidant, 0.02kg of lubricant and 0.002kg of stannous octoate.
[ example 4 ]
The preparation method of the antifogging TPU material of this example is the same as that of example 1, and is not described herein again, except that:
in this embodiment, the preparation method of the anti-fog TPU film includes:
step 1, carrying out a dissolving process on the antifogging TPU particles through an MEK solvent;
step 2, coating the dissolved TPU material on release paper or a polyester film through a coating process;
and 3, drying and coiling to obtain the antifogging TPU film with the thickness of 0.3 mm.
[ example 5 ]
The preparation methods of the antifogging TPU material and the antifogging TPU film of this embodiment are the same as those of embodiment 4, and are not described herein again, except that:
in step 1, the raw materials are prepared according to the following weight: 3.62kg of polyethylene glycol (PEG), 0.9kg of trimethylolpropane polyethylene glycol monomethyl ether (N120), 1.16kg of 1, 4-Butanediol (BDO), 0.14kg of dimethylolbutyric acid (DMBA), 0.14kg of polyethylene oxide (PEO), 4kg of isophorone diisocyanate (IPDI), 0.02kg of antioxidant, 0.02kg of lubricant and 0.002kg of stannous octoate.
[ example 6 ]
The preparation methods of the antifogging TPU material and the antifogging TPU film of this embodiment are the same as those of embodiment 4, and are not described herein again, except that:
in step 1, the raw materials are prepared according to the following weight: 3.15kg of polyethylene glycol (PEG), 0.78kg of trimethylolpropane polyethylene glycol monomethyl ether (N120), 1.347kg of 1, 4-Butanediol (BDO), 0.16kg of dimethylolbutyric acid (DMBA), 0.16kg of polyethylene oxide (PEO), 4.38kg of isophorone diisocyanate (IPDI), 0.02kg of antioxidant, 0.02kg of lubricant and 0.002kg of stannous octoate.
The antifogging TPU films of examples 1-6 were subjected to water contact angle, tear strength, normal temperature light transmittance, high temperature light transmittance (90 ℃/5hr) and low temperature light transmittance (-5 ℃/24hr) tests, the test results are shown in the following table:
| test items | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 |
| Water contact angle ° | 9 | 18 | 45 | 8 | 20 | 46 |
| Tensile kg/cm2 | 126 | 206 | 355 | 106 | 198 | 342 |
| Transmittance at room temperature% | 92 | 90 | 90 | 94 | 92 | 93 |
| High temperature light transmittance% | 88 | 80 | 68 | 90 | 82 | 61 |
| Low temperature light transmittance% | 90 | 84 | 60 | 90 | 79 | 60 |
TABLE 1
It can be seen that as the proportion of the glycol raw materials (i.e., polyethylene glycol and trimethylolpropane polyethylene glycol monomethyl ether) is reduced, the proportion of the chain extender (i.e., 1, 4-butanediol, dimethylolbutyric acid and polyethylene oxide) is increased, the hydrophilicity (anti-fog effect) of the TPU film is poorer, and the high-temperature light transmittance and the low-temperature light transmittance are lower. In addition, the properties of TPU films formed by the lamination process and the coating process are similar.
The above-described embodiments are merely preferred examples of the present invention, and not intended to limit the scope of the invention, so that equivalent changes or modifications in the structure, features and principles of the invention described in the claims should be included in the claims.
Claims (10)
1. A preparation method of an antifogging TPU material is characterized by comprising the following steps: the preparation method comprises the following steps:
step 1, preparing raw materials according to the following proportions: 30-55% of polyethylene glycol, 10-20% of trimethylolpropane polyethylene glycol monomethyl ether, 3-20% of 1, 4-butanediol, 1-5% of dimethylolbutyric acid, 1-5% of polyethylene oxide, 15-45% of isophorone diisocyanate, and 1-3% of antioxidant, lubricant and stannous octoate in total;
step 2, carrying out negative pressure dehydration treatment on 1, 4-butanediol, dimethylolbutyric acid and polyethylene oxide until the water content is below 100 PPM;
step 3, stirring and mixing the raw materials at the temperature of 90 ℃;
step 4, baking the mixed raw materials, and cooling to normal temperature;
and 5, crushing the mixed raw materials, and performing an extrusion process to form the antifogging TPU material.
2. The preparation method of the antifog TPU material of claim 1, characterized in that: in step 1, the hydroxyl value of polyethylene glycol is 37-120, the hydroxyl value of trimethylolpropane polyethylene glycol monomethyl ether is 112, and the hydroxyl value of polyethylene oxide is 540-580.
3. The preparation method of the antifog TPU material of claim 1, characterized in that: in the step 1, the ratio of the total ratio of the composite chain extender of hydroxymethylbutyric acid and polyethylene oxide to the ratio of the chain extender of 1, 4-butanediol is 4: 6.
4. the preparation method of the antifog TPU material of claim 1, characterized in that: in step 1, the antioxidant is one or more of antioxidant BHT, antioxidant 1010, antioxidant 1076 and antioxidant 168.
5. The preparation method of the antifog TPU material of claim 1, characterized in that: in step 1, the lubricant is one or two of paraffin and stearic acid.
6. The preparation method of the antifog TPU material of claim 1, characterized in that: in step 2, the degree of vacuum in the negative pressure water removal process is less than 2 Torr.
7. The preparation method of the antifog TPU material of claim 1, characterized in that: the step 3 specifically comprises the following steps:
step 3.1, inputting nitrogen into the stirring device, maintaining the air pressure of 0.1MPa, heating to 90 ℃, pouring polyethylene glycol, trimethylolpropane polyethylene glycol monomethyl ether, isophorone diisocyanate, an antioxidant, a lubricant and stannous octoate, stirring, and reacting for 2 hours;
step 3.2, cooling to 70 ℃, pouring 1, 4-butanediol, dimethylolbutyric acid and polyethylene oxide, stirring, and reacting for 1-2 hours;
and 3.3, filling the mixture into a polypropylene disk container.
8. The preparation method of the antifog TPU material of claim 1, characterized in that: the step 4 specifically comprises the following steps:
step 4.1, placing the mixed raw materials into an oven, heating to 90 ℃, vacuumizing by using a vacuum pump, and maintaining the vacuum degree of 650mmHg for 5 hours;
step 4.2, raising the temperature to 105 ℃, keeping the vacuum degree at 650mmHg, and maintaining for 2 hours;
step 4.3, changing the vacuum degree to 750mmHg, heating to 140 ℃, and maintaining for 3 hours;
and 4.4, closing the oven, and standing the mixed raw materials.
9. A preparation method of an antifogging TPU film is characterized by comprising the following steps: the preparation method comprises the following steps:
step 1, carrying out a casting process on the antifogging TPU material of claim 1 through a casting machine;
step 2, spraying the molten TPU material on release paper or a polyester film through a film spraying process;
and 3, cooling, shaping and coiling to obtain the antifogging TPU film.
10. A preparation method of an antifogging TPU film is characterized by comprising the following steps: the preparation method comprises the following steps:
step 1, carrying out a dissolving process on the antifogging TPU material of claim 1 through a solvent;
step 2, coating the dissolved TPU material on release paper or a polyester film through a coating process;
and 3, drying and coiling to obtain the antifogging TPU film.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114230841A (en) * | 2021-12-30 | 2022-03-25 | 深圳南科新材科技有限公司 | Polyurethane antifogging film and preparation method thereof |
| CN116284679A (en) * | 2023-05-18 | 2023-06-23 | 山东一诺威聚氨酯股份有限公司 | Super-hydrophilic anti-fog thermoplastic polyurethane elastomer material and preparation method and application thereof |
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| CN116284679A (en) * | 2023-05-18 | 2023-06-23 | 山东一诺威聚氨酯股份有限公司 | Super-hydrophilic anti-fog thermoplastic polyurethane elastomer material and preparation method and application thereof |
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