CN113307944A - Preparation method of hard fluorine-containing polyurethane with hierarchical pore structure - Google Patents
Preparation method of hard fluorine-containing polyurethane with hierarchical pore structure Download PDFInfo
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- CN113307944A CN113307944A CN202110606129.7A CN202110606129A CN113307944A CN 113307944 A CN113307944 A CN 113307944A CN 202110606129 A CN202110606129 A CN 202110606129A CN 113307944 A CN113307944 A CN 113307944A
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 44
- 239000011737 fluorine Substances 0.000 title claims abstract description 44
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 35
- 239000004814 polyurethane Substances 0.000 title claims abstract description 35
- 239000002149 hierarchical pore Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000000839 emulsion Substances 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 14
- OXBLVCZKDOZZOJ-UHFFFAOYSA-N 2,3-Dihydrothiophene Chemical compound C1CC=CS1 OXBLVCZKDOZZOJ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000000977 initiatory effect Effects 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 17
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 15
- 239000000047 product Substances 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- -1 mercapto compound Chemical class 0.000 claims description 11
- 239000000178 monomer Substances 0.000 claims description 11
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 10
- 229920000570 polyether Polymers 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 229920005862 polyol Polymers 0.000 claims description 8
- 150000003077 polyols Chemical class 0.000 claims description 8
- 239000004094 surface-active agent Substances 0.000 claims description 8
- FEWFXBUNENSNBQ-UHFFFAOYSA-N 2-hydroxyacrylic acid Chemical compound OC(=C)C(O)=O FEWFXBUNENSNBQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000004970 Chain extender Substances 0.000 claims description 6
- JOBBTVPTPXRUBP-UHFFFAOYSA-N [3-(3-sulfanylpropanoyloxy)-2,2-bis(3-sulfanylpropanoyloxymethyl)propyl] 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(COC(=O)CCS)(COC(=O)CCS)COC(=O)CCS JOBBTVPTPXRUBP-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000012948 isocyanate Substances 0.000 claims description 6
- 150000002513 isocyanates Chemical class 0.000 claims description 6
- 230000001376 precipitating effect Effects 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 230000001678 irradiating effect Effects 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 4
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 claims description 4
- MOTZDAYCYVMXPC-UHFFFAOYSA-N dodecyl hydrogen sulfate Chemical compound CCCCCCCCCCCCOS(O)(=O)=O MOTZDAYCYVMXPC-UHFFFAOYSA-N 0.000 claims description 4
- 229940043264 dodecyl sulfate Drugs 0.000 claims description 4
- 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 4
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 3
- DEQJNIVTRAWAMD-UHFFFAOYSA-N 1,1,2,4,4,4-hexafluorobutyl prop-2-enoate Chemical compound FC(F)(F)CC(F)C(F)(F)OC(=O)C=C DEQJNIVTRAWAMD-UHFFFAOYSA-N 0.000 claims description 3
- QTKPMCIBUROOGY-UHFFFAOYSA-N 2,2,2-trifluoroethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)F QTKPMCIBUROOGY-UHFFFAOYSA-N 0.000 claims description 3
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 claims description 3
- CDXFIRXEAJABAZ-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F CDXFIRXEAJABAZ-UHFFFAOYSA-N 0.000 claims description 3
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 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
- 238000004140 cleaning Methods 0.000 claims description 2
- 238000012650 click reaction Methods 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 150000005846 sugar alcohols Polymers 0.000 claims description 2
- TYCFGHUTYSLISP-UHFFFAOYSA-N 2-fluoroprop-2-enoic acid Chemical compound OC(=O)C(F)=C TYCFGHUTYSLISP-UHFFFAOYSA-N 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 238000006116 polymerization reaction Methods 0.000 description 5
- 238000010276 construction Methods 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LCPUCXXYIYXLJY-UHFFFAOYSA-N 1,1,2,4,4,4-hexafluorobutyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(F)(F)C(F)CC(F)(F)F LCPUCXXYIYXLJY-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 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
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
Classifications
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- 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
- C08G18/83—Chemically modified polymers
- C08G18/834—Chemically modified polymers by compounds containing a thiol group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—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
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
-
- 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
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 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
- 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
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
-
- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
-
- 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)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention provides a preparation method of hard fluorine-containing polyurethane with a hierarchical pore structure, which comprises the following steps: s1, designing and constructing a high internal phase emulsion system; s2, initiating the thiol-ene click chemistry reaction of the high internal phase emulsion. The preparation method of the hard fluorine-containing polyurethane with the hierarchical pore structure has the following technical advantages: (1) the invention provides a method for efficiently introducing fluorine-containing groups into rigid polyurethane with a hierarchical pore structure, and provides a new effective way for high-value utilization of the fluorine-containing groups; (2) the invention develops a novel synthesis technology for successfully and efficiently preparing the hard fluorine-containing polyurethane material with the hierarchical pore structure by combining the mercapto-alkene click chemistry with a high internal phase emulsion template method; (3) the method has the advantages of cheap and easily-obtained raw materials, simple operation method, mild and easily-controlled conditions, environmental protection, low production cost and easy industrial production.
Description
Technical Field
The invention relates to a preparation method of a rigid polyurethane material with a hierarchical pore structure, in particular to a preparation method for efficiently introducing fluorine-containing groups into a rigid polyurethane material structure with a hierarchical pore structure, belonging to the technical field of fluorine-containing chemicals and new materials.
Background
Polyurethane (Polyurethane) is a novel engineering material and is widely applied to various fields of national economy due to excellent performance. The rigid polyurethane material with the hierarchical pore structure is widely applied to the aspects of building industry, transportation industry, petrochemical industry, food storage, household appliances and the like due to the characteristics of large specific surface area, small heat conductivity coefficient, good heat insulation performance, high structural strength, small density, light weight, good shockproof and sound insulation effects, excellent weather resistance, stable chemical performance and the like, is closely related to the civil engineering, and is a novel engineering material acknowledged in the 21 st century.
However, most of the conventional rigid polyurethane materials contain hydrophilic groups, which results in the deterioration of water resistance, solvent resistance and the like. Fluorine has a shielding effect, a minimum polarizability, and the strongest electronegativity of all known elements, and thus fluorine-containing rigid polyurethane materials exhibit excellent properties such as hydrophobicity, lubricity, weather resistance, and better mechanical properties and biocompatibility. However, the poor solubility of the fluorine-containing monomer leads to complex conditions, high cost and unsatisfactory comprehensive properties of the material in the conventional synthesis method for constructing polyurethane by using the fluorine-containing monomer as a soft segment or a hard segment. In addition, therefore, the existing method for copolymerizing the photo-initiated polyurethane prepolymer and the fluorine-containing acrylic acid monomer not only has the problem of low solubility of the fluorine-containing acrylate in water, but also has the defects of easy oxygen inhibition in the polymerization process, low crosslinking density of the product and poor mechanical property.
Therefore, it is necessary to provide a further solution to the above problems.
Disclosure of Invention
The invention aims to provide a preparation method for successfully and efficiently introducing fluorine-containing groups into a rigid polyurethane structure with a hierarchical pore structure, so as to overcome the problems in the prior art.
To achieve the above object, the present invention provides a method for efficiently introducing fluorine-containing groups into a rigid polyurethane structure having a hierarchical pore structure, comprising the steps of:
s1, designing and constructing a high internal phase emulsion system:
the step S1 includes:
s10, preparing a double-bond-terminated polyurethane prepolymer by using isocyanate as a hard segment, polyether polyol as a soft segment, 1, 4-butanediol as a chain extender and hydroxy acrylic acid as a terminal resin;
s11, mixing the polyurethane prepolymer with a fluorine-containing acrylic monomer, a mercapto compound, a surfactant and deionized water at a certain temperature and a certain stirring speed to prepare a stable high internal phase emulsion system;
s2, initiating thiol-ene click chemistry of high internal phase emulsion:
the step S2 includes:
s20, adding a photoinitiator into the high internal phase emulsion system constructed in the step S1, mixing for a certain time at a certain temperature and stirring speed, placing the mixture into an ultraviolet lamp box, carrying out ultraviolet reaction for a certain time at a wavelength of 365nm, and carrying out mercapto-alkene click reaction in the system to obtain an initial product;
and S21, repeatedly cleaning the initial product obtained in the step S20, and then drying in vacuum to obtain a final product.
As an improvement of the method for preparing the rigid fluorine-containing polyurethane with the hierarchical pore structure, in the step S10, the isocyanate is one of isophorone diisocyanate, diphenylmethane diisocyanate, and toluene diisocyanate; the polyalcohol is one of polyether DL1000, 2000LM, TMN450 and TMN 3050; the chain extender is 1, 4-butanediol; the hydroxy acrylic acid is one of hydroxyethyl methacrylate, hydroxyethyl acrylate and hydroxypropyl methacrylate; the usage amount of the isocyanate is 8.0-28.0 parts, the usage amount of the polyether polyol is 37.0-57.0 parts, the usage amount of the chain extender is 10.0-20.0 parts, and the usage amount of the hydroxyacrylic acid is 5.0-15.0 parts.
As an improvement of the method for preparing the rigid fluorine-containing polyurethane with the hierarchical pore structure, in the step S11, the fluorine-containing acrylic monomer is one of trifluoroethyl methacrylate, hexafluorobutyl acrylate and 2- (perfluorohexyl) ethyl methacrylate; the mercapto compound is pentaerythritol tetrakis (3-mercaptopropionate); the surfactant is one or two of span 80, 1-alkyl-3-methylimidazole dodecyl sulfate and 1-butyl-3-methylimidazole di-ethylhexyl succinate sulfonate; the polyurethane prepolymer is prepared from 8.0-13.0 parts of deionized water 72.0-84.0 parts of fluorine-containing acrylic monomer 3.0-5.0 parts of mercapto compound 3.0-5.0 parts of surfactant 1.0-3.0 parts of the prepolymer.
As an improvement of the preparation method of the hard fluorine-containing polyurethane with the hierarchical pore structure, in the step S11, the polyurethane prepolymer is mixed with the fluorine-containing acrylic monomer, the mercapto compound, the surfactant and the deionized water at the temperature of 50-70 ℃ and the rotation speed of 400-600rpm and stirred for 3-30 minutes.
As an improvement of the method for preparing the rigid fluorine-containing polyurethane having a hierarchical pore structure according to the present invention, in step S20, the photoinitiator is one of 2-hydroxy-2-methyl-1-phenyl-1-propanone, 4- (2-hydroxy-3-tert-butyl) benzophenone, and 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl ] propanone; the dosage of the photoinitiator is 1.0-2.0 parts.
As an improvement of the preparation method of the hard fluorine-containing polyurethane with the hierarchical pore structure, in the step S20, after the photoinitiator is added, mixing is carried out for 3-30 minutes at the temperature of 50-70 ℃ and the rotation speed of 400-600 rpm; and (3) irradiating the prepared high internal phase emulsion system under the ultraviolet light with the wavelength of 365nm for 1-10 minutes.
As an improvement of the method for preparing the rigid fluorine-containing polyurethane having a hierarchical pore structure according to the present invention, the step S21 specifically includes: and (3) washing and precipitating the initial product obtained in the step S20 by using water and ethanol alternately and repeatedly, and drying in vacuum to obtain the hard fluorine-containing polyurethane material with the hierarchical pore structure.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention provides a method for successfully introducing fluorine-containing groups into rigid polyurethane with a hierarchical pore structure, and provides a new effective way for high-value utilization of the fluorine-containing groups;
(2) the invention develops a novel synthesis technology for successfully and efficiently preparing the hard fluorine-containing polyurethane material with the hierarchical pore structure by combining the mercapto-alkene click chemistry with a high internal phase emulsion template method;
(3) the method has the advantages of cheap and easily-obtained raw materials, simple operation method, mild and easily-controlled conditions, environmental protection, low production cost and easy industrial production.
Detailed Description
The principles and features of this invention are described below in conjunction with examples, which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
Example 1:
s1, construction of a high internal phase emulsion system:
adding dehydrated polyether polyol 2000LM (37.0 parts by weight), diphenylmethane diisocyanate (28.0 parts by weight) and 1, 4-butanediol (20.0 parts by weight) into a three-necked bottle provided with a stirrer, a thermometer and a condenser in sequence, reacting at 50 ℃ until the-NCO content is qualified, adding polymerization inhibitor treated hydroxyethyl acrylate (15.0 parts by weight) and reacting at 60 ℃ until the NCO content is less than or equal to 0.1% to obtain the polyurethane prepolymer. At 50 ℃, mixing the prepared polyurethane prepolymer (13.0 parts by weight) with 5.0 parts by weight of hexafluorobutyl methacrylate, 5.0 parts by weight of pentaerythritol tetrakis (3-mercaptopropionate), 3.0 parts by weight of 1-alkyl-3-methylimidazol dodecyl sulfate and 72.0 parts by weight of deionized liquid water at the rotating speed of 600rpm to prepare a stable high internal phase emulsion system;
s2, initiating thiol-ene click chemistry of high internal phase emulsion:
in the high internal phase emulsion system prepared in step S1, a photoinitiator 4- (2-hydroxy-3-tert-butyl) benzophenone (2.0 parts by weight) is added in an amount of 50oC, mixing for 30 minutes at the rotating speed of 600 rpm; placing the high internal phase emulsion system under an ultraviolet lamp with the wavelength of 365nm for irradiating for 10 minutes, and curing to obtain a primary product; and washing and precipitating the primary product by using water and ethanol alternately and repeatedly, and drying in vacuum to obtain the hard fluorine-containing polyurethane with a porous structure.
Example 2:
s1, construction of a high internal phase emulsion system:
and (2) sequentially adding dehydrated polyether polyol DL1000 (57.0 parts by weight), isophorone diisocyanate (18.0 parts by weight) and 1, 4-butanediol (15.0 parts by weight) into a three-necked bottle provided with a stirrer, a thermometer and a condenser, reacting at 50 ℃ until the-NCO content is qualified, adding polymerization inhibitor treated hydroxyethyl methacrylate (10.0 parts by weight), and reacting at 60 ℃ until the NCO content is less than or equal to 0.1% to obtain the polyurethane prepolymer. Mixing 8.0 parts by weight of the prepared polyurethane prepolymer with 3.0 parts by weight of trifluoroethyl methacrylate, 3.0 parts by weight of pentaerythritol tetrakis (3-mercaptopropionate), 1.0 part by weight of span 80 and 84.0 parts by weight of deionized liquid water at the rotating speed of 400rpm to prepare a stable high internal phase emulsion system at the temperature of 70 ℃;
s2, initiating thiol-ene click chemistry of high internal phase emulsion:
in the high internal phase emulsion system prepared in step S1, 2-hydroxy-2-methyl-1-phenyl-1-propanone (1.0 part by weight) as a photoinitiator was added at 70 deg.CoC, mixing for 17 minutes at the rotating speed of 400 rpm; placing the high internal phase emulsion system under an ultraviolet lamp with the wavelength of 365nm for irradiating for 5 minutes, and curing to obtain a primary product; and washing and precipitating the primary product by using water and ethanol alternately and repeatedly, and drying in vacuum to obtain the hard fluorine-containing polyurethane with a porous structure.
Example 3:
s1, construction of a high internal phase emulsion system:
adding dehydrated polyether polyol TMN450 (47.0 parts by weight), toluene diisocyanate (23.0 parts by weight) and 1, 4-butanediol (17.5 parts by weight) into a three-necked bottle provided with a stirrer, a thermometer and a condenser in sequence, reacting at 50 ℃ until the-NCO content is qualified, adding polymerization inhibitor treated hydroxypropyl methacrylate (12.5 parts by weight) and reacting at 60 ℃ until the NCO content is less than or equal to 0.1% to obtain the polyurethane prepolymer. Mixing the prepared polyurethane prepolymer (10.5 parts by weight) with hexafluorobutyl acrylate (4.0 parts by weight), pentaerythritol tetrakis (3-mercaptopropionate) (4.0 parts by weight), 1-butyl-3-methylimidazol di-ethylhexyl succinate sulfonate (2.0 parts by weight) and deionized liquid water (78.0 parts by weight) at the rotating speed of 500rpm at the temperature of 60 ℃ to prepare a stable high internal phase emulsion system;
s2, initiating thiol-ene click chemistry of high internal phase emulsion:
adding a photoinitiator 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl group into the high internal phase emulsion system prepared in the step S1]Acetone (1.5 parts by weight) at 60oC, mixing for 3 minutes at the rotating speed of 500 rpm; placing the high internal phase emulsion system under an ultraviolet lamp with the wavelength of 365nm for irradiating for 1 minute, and curing to obtain a primary product; and washing and precipitating the primary product by using water and ethanol alternately and repeatedly, and drying in vacuum to obtain the hard fluorine-containing polyurethane with a porous structure.
Example 4:
s1, construction of a high internal phase emulsion system:
adding dehydrated polyether polyol TMN3050 (37.0 parts by weight), isophorone diisocyanate (28.0 parts by weight) and 1, 4-butanediol (20.0 parts by weight) into a three-necked bottle provided with a stirrer, a thermometer and a condenser in sequence, reacting at 50 ℃ until the-NCO content is qualified, adding hydroxyethyl acrylate (15.0 parts by weight) treated by a polymerization inhibitor, and reacting at 60 ℃ until the NCO content is less than or equal to 0.1% to obtain the polyurethane prepolymer. At 50 ℃, mixing 13.0 parts by weight of the prepared polyurethane prepolymer with 5.0 parts by weight of 2- (perfluorohexyl) ethyl methacrylate, 5.0 parts by weight of pentaerythritol tetrakis (3-mercaptopropionate), 1.5 parts by weight of span 80, 1-alkyl-3-methylimidazol dodecyl sulfate and 72.0 parts by weight of deionized liquid water at the rotating speed of 600rpm to prepare a stable high internal phase emulsion system;
s2, initiating thiol-ene click chemistry of high internal phase emulsion:
in the high internal phase emulsion system prepared in step S1, a photoinitiator 4- (2-hydroxy-3-tert-butyl) benzophenone (2.0 parts by weight) is added in an amount of 50oC, mixing for 30 minutes at the rotating speed of 600 rpm; placing the high internal phase emulsion system under 365nm ultraviolet lampIrradiating for 10 minutes, and curing to obtain a primary product; and washing and precipitating the primary product by using water and ethanol alternately and repeatedly, and drying in vacuum to obtain the hard fluorine-containing polyurethane with a porous structure.
In summary, the preparation method of the hard fluorine-containing polyurethane with the hierarchical pore structure has the following technical advantages:
(1) the invention provides a method for successfully introducing fluorine-containing groups into rigid polyurethane with a hierarchical pore structure, and provides a new effective way for high-value utilization of the fluorine-containing groups; (2) the invention develops a novel synthesis technology for successfully and efficiently preparing the hard fluorine-containing polyurethane material with the hierarchical pore structure by combining the mercapto-alkene click chemistry with a high internal phase emulsion template method; (3) the method has the advantages of cheap and easily-obtained raw materials, simple operation method, mild and easily-controlled conditions, environmental protection, low production cost and easy industrial production.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (7)
1. A preparation method of hard fluorine-containing polyurethane with a hierarchical pore structure is characterized by comprising the following steps:
s1, designing and constructing a high internal phase emulsion system:
the step S1 includes:
s10, preparing a double-bond-terminated polyurethane prepolymer by using isocyanate as a hard segment, polyether polyol as a soft segment, 1, 4-butanediol as a chain extender and hydroxy acrylic acid as a terminal resin;
s11, mixing the polyurethane prepolymer with a fluorine-containing acrylic monomer, a mercapto compound, a surfactant and deionized water at a certain temperature and a certain stirring speed to prepare a stable high internal phase emulsion system;
s2, initiating thiol-ene click chemistry of high internal phase emulsion:
the step S2 includes:
s20, adding a photoinitiator into the high internal phase emulsion system constructed in the step S1, mixing for a certain time at a certain temperature and stirring speed, placing the mixture into an ultraviolet lamp box, carrying out ultraviolet reaction for a certain time at a wavelength of 365nm, and carrying out mercapto-alkene click reaction in the system to obtain an initial product;
and S21, repeatedly cleaning the initial product obtained in the step S20, and then drying in vacuum to obtain a final product.
2. The method of claim 1, wherein in the step S10, the isocyanate is one of isophorone diisocyanate, diphenylmethane diisocyanate, and toluene diisocyanate; the polyalcohol is one of polyether DL1000, 2000LM, TMN450 and TMN 3050; the chain extender is 1, 4-butanediol; the hydroxy acrylic acid is one of hydroxyethyl methacrylate, hydroxyethyl acrylate and hydroxypropyl methacrylate; the usage amount of the isocyanate is 8.0-28.0 parts, the usage amount of the polyether polyol is 37.0-57.0 parts, the usage amount of the chain extender is 10.0-20.0 parts, and the usage amount of the hydroxyacrylic acid is 5.0-15.0 parts.
3. The method according to claim 1, wherein in step S11, the fluorine-containing acrylic monomer is one of trifluoroethyl methacrylate, hexafluorobutyl acrylate, and 2- (perfluorohexyl) ethyl methacrylate; the mercapto compound is pentaerythritol tetrakis (3-mercaptopropionate); the surfactant is one or two of span 80, 1-alkyl-3-methylimidazole dodecyl sulfate and 1-butyl-3-methylimidazole di-ethylhexyl succinate sulfonate; the polyurethane prepolymer is prepared from 8.0-13.0 parts of deionized water 72.0-84.0 parts of fluorine-containing acrylic monomer 3.0-5.0 parts of mercapto compound 3.0-5.0 parts of surfactant 1.0-3.0 parts of the prepolymer.
4. The method as claimed in claim 1, wherein the step S11 comprises mixing the polyurethane prepolymer with the fluoroacrylic acid monomer, the mercapto compound, the surfactant, and the deionized water at a temperature of 50-70 ℃ and a rotation speed of 600rpm and stirring for 3-30 minutes.
5. The method of claim 1, wherein in the step S20, the photoinitiator is one of 2-hydroxy-2-methyl-1-phenyl-1-propanone, 4- (2-hydroxy-3-tert-butyl) benzophenone, and 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl ] propanone; the dosage of the photoinitiator is 1.0-2.0 parts.
6. The method for preparing a rigid fluorinated polyurethane having a hierarchical pore structure according to claim 1, wherein the step S20 comprises mixing at 400rpm and 50-70 ℃ for 3-30 minutes after adding the photoinitiator; and (3) irradiating the prepared high internal phase emulsion system under the ultraviolet light with the wavelength of 365nm for 1-10 minutes.
7. The method according to claim 1, wherein the step S21 specifically comprises: and (3) washing and precipitating the initial product obtained in the step S20 by using water and ethanol alternately and repeatedly, and drying in vacuum to obtain the hard fluorine-containing polyurethane material with the hierarchical pore structure.
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