CN117447678A - UVB-resistant and wear-resistant polyurethane resin containing acrylic chain segments and preparation method thereof - Google Patents
UVB-resistant and wear-resistant polyurethane resin containing acrylic chain segments and preparation method thereof Download PDFInfo
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- CN117447678A CN117447678A CN202311291046.9A CN202311291046A CN117447678A CN 117447678 A CN117447678 A CN 117447678A CN 202311291046 A CN202311291046 A CN 202311291046A CN 117447678 A CN117447678 A CN 117447678A
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- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 229920005749 polyurethane resin Polymers 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000000576 coating method Methods 0.000 claims abstract description 44
- 239000011248 coating agent Substances 0.000 claims abstract description 40
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000002904 solvent Substances 0.000 claims abstract description 18
- DJOWTWWHMWQATC-KYHIUUMWSA-N Karpoxanthin Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1(O)C(C)(C)CC(O)CC1(C)O)C=CC=C(/C)C=CC2=C(C)CC(O)CC2(C)C DJOWTWWHMWQATC-KYHIUUMWSA-N 0.000 claims abstract description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 11
- 229920000642 polymer Polymers 0.000 claims abstract description 11
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000012948 isocyanate Substances 0.000 claims abstract description 10
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 10
- 239000000178 monomer Substances 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 5
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000003112 inhibitor Substances 0.000 claims abstract description 5
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 12
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 10
- 238000005299 abrasion Methods 0.000 claims description 10
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 10
- 239000003153 chemical reaction reagent Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 229920001610 polycaprolactone Polymers 0.000 claims description 9
- 239000004632 polycaprolactone Substances 0.000 claims description 9
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 8
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 claims description 8
- 239000011521 glass Substances 0.000 claims description 8
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 7
- 229920000570 polyether Polymers 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 6
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 6
- 238000011049 filling Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229920000728 polyester Polymers 0.000 claims description 5
- 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 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 4
- 229940044119 2-tert-butylhydroquinone Drugs 0.000 claims description 4
- HIFVAOIJYDXIJG-UHFFFAOYSA-N benzylbenzene;isocyanic acid Chemical class N=C=O.N=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 HIFVAOIJYDXIJG-UHFFFAOYSA-N 0.000 claims description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000007787 solid Substances 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 2
- 235000010354 butylated hydroxytoluene Nutrition 0.000 claims description 2
- QZUFYZAIYPHVTL-UHFFFAOYSA-L diacetyloxy(butyl)tin Chemical compound CCCC[Sn](OC(C)=O)OC(C)=O QZUFYZAIYPHVTL-UHFFFAOYSA-L 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims 1
- 239000005977 Ethylene Substances 0.000 claims 1
- 239000005058 Isophorone diisocyanate Substances 0.000 claims 1
- 239000002131 composite material Substances 0.000 claims 1
- 239000011527 polyurethane coating Substances 0.000 abstract description 3
- 238000013461 design Methods 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 7
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 238000004321 preservation Methods 0.000 description 4
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 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 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 230000004224 protection Effects 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/81—Unsaturated isocyanates or isothiocyanates
- C08G18/8108—Unsaturated isocyanates or isothiocyanates having only one isocyanate or isothiocyanate group
- C08G18/8116—Unsaturated isocyanates or isothiocyanates having only one isocyanate or isothiocyanate group esters of acrylic or alkylacrylic acid having only one isocyanate or isothiocyanate 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
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4202—Two or more polyesters of different physical or chemical nature
-
- 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
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
-
- 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
- C08G18/4829—Polyethers containing at least three hydroxy groups
-
- 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
- C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
-
- 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
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
- C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a UVB-resistant and wear-resistant polyurethane resin containing an acrylic chain segment and a preparation method thereof, wherein the UVB-resistant and wear-resistant polyurethane resin consists of a component A and a component B according to the mass ratio of 2:1, wherein the component A is composed of 10-22% of oligomer triol, 5-15% of ethyl methacrylate, 7-25% of difunctional isocyanate monomer, 40-60% of solvent 1,0.01-0.1% of polymerization inhibitor, and the component B is composed of hydroxyl-containing polymer consisting of 3-1% of oligomer triol, 3-15% of oligomer tetrol, 2-8% of difunctional isocyanate monomer, 60-90% of solvent 2 and 0.01-0.1% of catalyst. The polyurethane coating containing the acrylic acid chain segment is synthesized through the design of a special structure, has good wear resistance, improves the ultraviolet irradiation performance of the coating in the UVB wave band by introducing the acrylic acid chain segment, and meets the wear resistance and the ultraviolet irradiation requirement of the aviation aircraft in the UVB wave band.
Description
Technical Field
The invention relates to the field of polyurethane resin, in particular to UVB-resistant and wear-resistant polyurethane resin containing acrylic chain segments and a preparation method thereof.
Background
The polyurethane resin has the advantages of high strength, tear resistance, wear resistance and the like, is widely applied to the fields of aviation, railway, medicine and the like, the surface of the transparent piece of the current aviation aircraft needs a wear-resistant transparent protective coating, and the polyurethane wear-resistant coating is firstly subjected to targeted research and mainly comprises means such as silicon modification research, wear-resistant particle hardening and the like, but has poor wear-resistant effect.
Meanwhile, because the aviation aircraft belongs to high-altitude operation, the aviation aircraft is easily irradiated by ultraviolet rays in UVB wave bands, and the molecular bonds of the coating resin are broken and destroyed, so that the protection effect is lost. Researchers mainly improve the irradiation performance of polyurethane coating against UVB wave band ultraviolet rays through resin modification and addition of various light stabilizers, and as patent CN202111108570.9 discloses fluorine-containing acrylic acid modified polyurethane wear-resistant resin and a preparation method thereof, a coating with good wear resistance and excellent irradiation resistance is prepared; patent CN202210343691.X discloses a polyurethane resin containing an inorganic ultraviolet absorbent and a preparation method thereof, and a coating with good wear resistance and QUV aging resistance is prepared by adding a modified inorganic ultraviolet absorbent.
At present, the ultraviolet resistance test of the coating is usually carried out by adopting traditional testing methods such as solar irradiation, artificial accelerated aging and the like, the coating is mainly damaged by UVA in a long wave band in near-earth sunlight, the energy is relatively small, the damage to the coating is small, and the modified coating can easily meet the testing requirements; however, for transparent parts of high-altitude aircrafts, the coating is mainly irradiated by ultraviolet rays in UVB wave bands, the energy is relatively large, the damage to the coating is extremely strong, and the quantitative assessment cannot be carried out by adopting a traditional testing method. Aiming at the performance test, the aviation material institute adopts an accelerated assessment test method of directly irradiating the coating with 313nm ultraviolet rays in order to better simulate the environment of the transparent part of the model aircraft. According to the conventional test results, the common wear-resistant polyurethane resin coating has the phenomenon of sticky damage after being irradiated for several hours or more than ten hours, and even the modified resin is difficult to meet the phenomenon that the coating is not sticky and damaged after being irradiated for 24 hours.
Disclosure of Invention
The invention prepares the UVB-resistant and wear-resistant polyurethane resin containing acrylic chain segments, creatively refers to a cage-shaped silsesquioxane (POSS) structure, synthesizes polyurethane cage-shaped polyol by adopting a specific process, and has the following structure:
the cage structure is similar to a football structure, when the cage structure is extruded by external force, the impact of the external force on the resin coating is reduced due to certain contractible rebound, and when the external force disappears, the cage structure can be restored to the original state, has self-repairing property, and can not cause coating abrasion due to the external force, so that the coating has good abrasion resistance. Meanwhile, a certain amount of double bonds are reserved in the coating by preparing the component A containing the acrylic chain segment, and due to instability of the double bonds, pi bonds in the double bonds are broken at first when the coating is irradiated by a 313nm ultraviolet lamp, so that ultraviolet heat can be continuously consumed, breakage of delta bonds of main molecules of the coating is avoided, the coating can meet the requirement that the phenomenon of sticky damage cannot occur after the continuous irradiation of 313nm ultraviolet for 24 hours, and the abrasion-resistant and ultraviolet-resistant protective effect on transparent parts of aviation aircrafts can be met.
The UVB-resistant and wear-resistant polyurethane resin containing the acrylic chain segment, which is prepared by the invention, is divided into two components, wherein the mass fractions of the components are as follows:
the mass fraction of each component in the component A (the acrylic chain segment-containing oligomer) and the preparation method are as follows:
the oligomer triol is one of polyester triol, polycaprolactone triol and polyether triol.
The difunctional isocyanate monomer is one or two of isophorone diisocyanate (IPDI), toluene Diisocyanate (TDI) and hydrogenated diphenylmethane diisocyanate (H12 MDI).
The solvent 1 is one or more of acetone, toluene and butyl acetate.
The polymerization inhibitor is one or two of hydroquinone, p-hydroxyanisole, 2, 6-di-tert-butyl p-cresol, 2-tert-butyl hydroquinone and 2-tert-butyl hydroquinone.
The preparation method of the component A (the oligomer containing the acrylic chain segment) comprises the following steps:
the first step: adding oligomer triol into a reaction container, heating to enable the system to be placed in a 60 ℃ environment, dropwise adding ethyl methacrylate under stirring, keeping the dropwise adding speed at 2 drops/second, continuously preserving heat for 2 hours after dropwise adding, then heating to 80 ℃ in a gradient way (heating rate of 10 ℃/min), continuously preserving heat for 2 hours at the temperature of 80 ℃, cooling, adding a solvent 1 and a polymerization inhibitor, discharging, filling into a brown reagent bottle, and preserving for standby under the condition of not exceeding room temperature.
And a second step of: adding difunctional isocyanate monomer into a reaction vessel, heating to enable the system to be in a 60 ℃ environment, dropwise adding the product of the first step under the condition of stirring, keeping the dropwise adding speed at 2 drops/second, heating to 80 ℃ after the dropwise adding is finished, keeping the temperature for 2 hours at 90 ℃, naturally cooling to room temperature, adding solvent 1, continuously stirring for 10 minutes, and obtaining the component A (the oligomer containing the acrylic chain segment), and then filling into a brown reagent bottle and storing under the condition of not exceeding the room temperature.
The mass fraction of each component in the component B (hydroxyl-containing polymer) and the preparation method thereof are as follows:
the oligomer triol is one of polyester triol, polycaprolactone triol and polyether triol.
The oligomer tetrol is one of polyester tetrol, polycaprolactone tetrol and polyether tetrol.
The solvent 2 is one or more of ethyl acetate, butyl acetate, xylene, cyclohexanone and butanone.
The catalyst is one of dibutyl tin dilaurate, dibutyl tin dilaurate and butyl tin diacetate.
The preparation method of the component B (hydroxyl-containing polymer) comprises the following steps:
mixing oligomer triol and tetraol, adding the mixture into a reaction container, heating to enable the system to be placed in a 60 ℃ environment, adding a catalyst, dropwise adding difunctional isocyanate monomer and the mixture of the difunctional isocyanate monomer and the equal amount of solvent 2 under the condition of stirring, keeping the dropwise adding speed at 2 drops/second, adding all the rest solvent 2 after the dropwise adding is finished, heating until the solvent is distilled off, stopping heating when the solid content of the system reaches 50%, and cooling to obtain the component B (hydroxyl-containing polymer).
The preparation method of the UVB-resistant and wear-resistant polyurethane resin coating containing the acrylic chain segment comprises the following steps:
and mixing the prepared component A and component B according to the mass ratio of 2:1, stirring and reacting for 0.5h, standing, coating on an organic glass plate by adopting a flow coating process after bubbles disappear, and transferring the coating to a constant temperature drying oven after the surface of the coating is dried and baking at 80 ℃ for at least 5h to obtain the UVB-resistant and wear-resistant polyurethane resin coating containing the acrylic chain segments.
The beneficial effects of the invention are as follows:
the polyurethane coating containing the acrylic acid chain segment is synthesized through the design of a special structure, has good wear resistance, improves the ultraviolet irradiation performance of the coating in the UVB wave band by introducing the acrylic acid chain segment, and meets the wear resistance and the ultraviolet irradiation requirement of the aviation aircraft in the UVB wave band.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, based on the examples herein, which are within the scope of the invention, will be within the purview of one of ordinary skill in the art without the exercise of inventive faculty.
Example 1:
(1) Preparation of the A component (acrylic segment-containing oligomer):
a:48g of polycaprolactone triol is put into a reaction vessel, the reaction vessel is heated to enable the system to be placed in a 60 ℃ environment, 16g of ethyl methacrylate is dripped under the stirring condition, the dripping speed is kept at 2 drops/second, the heat preservation is continued for 2 hours after the dripping is finished, then the gradient temperature is increased to 80 ℃ (the heating rate is 10 ℃/min), the heat preservation reaction is continued for 2 hours at the temperature of 80 ℃, 70g of butyl acetate and 0.1g of hydroquinone are added after the cooling, the mixture is stirred evenly, discharged, filled into a brown reagent bottle and stored for standby under the condition of not exceeding room temperature.
b: adding 53g of hydrogenated diphenylmethane diisocyanate (H12 MDI) into a reaction vessel, heating the system to 60 ℃, dropwise adding the product in the step a under stirring, keeping the dropwise adding speed at 2 drops/second, heating to 80 ℃ after the dropwise adding is finished, keeping the temperature for 2 hours at 90 ℃, naturally cooling to room temperature, adding 50g of butyl acetate, continuously stirring for 10 minutes, and obtaining a component A (an acrylic acid segment-containing oligomer), and then filling into a brown reagent bottle and keeping the bottle under the condition of not exceeding room temperature.
Preparation of component B (hydroxyl-containing Polymer): mixing 30g of polycaprolactone triol and 47g of polycaprolactone tetrol, adding the mixture into a reaction vessel, heating to enable the system to be placed in a 60 ℃ environment, adding 0.1g of dibutyltin dilaurate, dropwise adding a mixture of 20.5g of hydrogenated diphenylmethane diisocyanate and 20.5g of butyl acetate under stirring, keeping the dropwise adding speed at 2 drops/second, adding the rest 200g of butyl acetate after the dropwise adding, heating to evaporate 123g of solvent, stopping heating until the solid content of the system reaches 50%, and cooling to obtain the component B (hydroxyl-containing polymer).
(2) Preparation of a UVB-resistant and wear-resistant polyurethane resin coating containing an acrylic chain segment: and mixing the component A and the component B according to the proportion of 2:1, stirring and reacting for 0.5h, standing, coating on an organic glass plate by adopting a flow coating process after bubbles disappear, and transferring the organic glass plate to a constant temperature drying oven after the surface of the coating is dried, and baking at 80 ℃ for at least 5h to obtain the UVB and wear resistant polyurethane resin coating containing the acrylic chain segments.
Example 2:
(1) Preparation of the A component (acrylic segment-containing oligomer):
a:53g of polyether triol PPG800 is added into a reaction vessel, the reaction vessel is heated to enable the system to be placed in a 60 ℃ environment, 22g of ethyl methacrylate is dripped under the stirring condition, the dripping speed is kept at 2 drops/second, the heat preservation is continued for 2 hours after the dripping is finished, then the gradient temperature is increased to 80 ℃ (the heating rate is 10 ℃/min), the heat preservation reaction is continued for 2 hours at the temperature of 80 ℃, then 80g of dimethylbenzene and 0.1g of hydroquinone are added in a cooling mode, the mixture is stirred evenly, discharged, filled into a brown reagent bottle and stored for standby under the condition of not exceeding room temperature.
b: adding 44g of TDI into a reaction vessel, heating the system to 60 ℃, dropwise adding the product of the step a under stirring, keeping the dropwise adding speed at 2 drops/second, heating to 80 ℃ after the dropwise adding, keeping the temperature for 2 hours at 90 ℃, naturally cooling to room temperature, adding 56g of butyl acetate, continuously stirring for 10 minutes, and obtaining the component A (the oligomer containing the acrylic acid chain segment), and then filling into a brown reagent bottle and storing under the condition of not exceeding the room temperature.
(2) Preparation of component B (hydroxyl-containing Polymer): 27g of polyether triol PPG800 and 47g of polycaprolactone tetrol are mixed and added into a reaction vessel, the system is heated to be placed in a 60 ℃ environment, 0.1g of dibutyltin dilaurate is added, 18g of TDI and a mixture with 18g of dimethylbenzene are dropwise added under stirring, the dropwise acceleration is kept at 2 drops/second, the rest 218g of butyl acetate is added after the dropwise addition, 144g of solvent is distilled off after heating, the solid content of the system reaches 50%, and the component B (hydroxyl-containing polymer) can be obtained after stopping heating and cooling.
(3) Preparation of UVB-resistant and wear-resistant polyurethane resin containing acrylic chain segments: and mixing the component A and the component B according to the proportion of 2:1, stirring and reacting for 0.5h, standing, coating on an organic glass plate by adopting a flow coating process after bubbles disappear, and transferring the organic glass plate to a constant temperature drying oven after the surface of the coating is dried, and baking at 80 ℃ for at least 5h to obtain the UVB and wear resistant polyurethane resin coating containing the acrylic chain segments.
The UVB-resistant and abrasion-resistant polyurethane resin coating containing the acrylic segment prepared above was subjected to irradiation with a 313nm ultraviolet lamp for 24 hours and abrasion resistance testing using the Q/6S1204 standard, and the results are shown in table 1 below:
table 1 example test results
The haze of the blank organic glass plate was 0.
Note that: the Q/6S1204 standard is an enterprise standard established by the aviation materials institute (621) of Beijing, fang, china, and the name is: the main test method is that after 200 times of erosion is carried out on the surface of the coating by using quartz sand with a specific model, the haze of the coating is tested, and the smaller the haze is, the better the wear resistance of the coating is indicated; the worse the reverse is.
The present disclosure has been described with respect to the above-described embodiments, however, the above-described embodiments are merely examples of implementation of the present disclosure. It must be noted that the disclosed embodiments do not limit the scope of the present disclosure. Rather, the foregoing is considered to be illustrative, and it is to be understood that the invention is not limited to the specific details disclosed herein.
Claims (7)
1. A UVB-resistant and wear-resistant polyurethane resin containing an acrylic chain segment is characterized in that: the composite material consists of a component A and a component B according to the mass ratio of 2:1, wherein the component A and the oligomer containing the acrylic chain segment consist of the following components:
the component B and the hydroxyl-containing polymer consist of the following components: :
2. the UVB resistant and abrasion resistant polyurethane resin containing acrylic segments according to claim 1, wherein: the oligomer triol is one of polyester triol, polycaprolactone triol and polyether triol; the oligomer tetrol is one of polyester tetrol, polycaprolactone tetrol and polyether tetrol.
3. The UVB resistant and abrasion resistant polyurethane resin containing acrylic segments according to claim 1, wherein: the difunctional isocyanate monomer is one or two of isophorone diisocyanate, toluene diisocyanate and hydrogenated diphenylmethane diisocyanate.
4. The UVB resistant and abrasion resistant polyurethane resin containing acrylic segments according to claim 1, wherein: the solvent 1 is one or more of acetone, toluene and butyl acetate; the solvent 2 is one or more of ethyl acetate, butyl acetate, xylene, cyclohexanone and butanone.
5. The UVB resistant and abrasion resistant polyurethane resin containing acrylic segments according to claim 1, wherein: the polymerization inhibitor is one or two of hydroquinone, p-hydroxyanisole, 2, 6-di-tert-butyl p-cresol, 2-tert-butyl hydroquinone and 2-tert-butyl hydroquinone.
6. The UVB resistant and abrasion resistant polyurethane resin containing acrylic segments according to claim 1, wherein: the catalyst is one of dibutyl tin dilaurate, dibutyl tin dilaurate and butyl tin diacetate.
7. A preparation method of UVB-resistant and wear-resistant polyurethane resin containing acrylic chain segments is characterized by comprising the following steps: the method is characterized by comprising the following steps of:
(1) Preparation of component A and the oligomer containing the acrylic chain segment:
a: adding oligomer triol into a reaction container, heating to enable the system to be placed in a 60 ℃ environment, dropwise adding ethyl methacrylate under the condition of stirring, keeping the dropwise adding speed at 2 drops/second, continuously preserving heat for 2 hours after the dropwise adding is finished, then gradually heating to 80 ℃ (the heating rate is 10 ℃/min), continuously preserving heat for 2 hours at the temperature of 80 ℃, then cooling, adding a solvent 1 and a polymerization inhibitor, discharging, filling into a brown reagent bottle, and preserving for standby under the condition of not exceeding room temperature;
b: adding difunctional isocyanate monomer into a reaction container, heating to enable the system to be in a 60 ℃ environment, dropwise adding the product of the first step under the condition of stirring, keeping the dropwise adding speed at 2 drops/second, heating to 80 ℃ after the dropwise adding is finished, keeping the temperature for 2 hours at 90 ℃, naturally cooling to room temperature, adding the solvent 1, continuously stirring for 10 minutes, obtaining a component A, and then filling the component A into a brown reagent bottle and keeping the reagent bottle under the condition of not exceeding the room temperature;
(2) Preparing a component B and a hydroxyl-containing polymer:
mixing oligomer triol and tetraol, adding the mixture into a reaction container, heating to enable the system to be placed in a 60 ℃ environment, adding a catalyst, dropwise adding difunctional isocyanate monomer and the mixture of the difunctional isocyanate monomer and the equal amount of solvent 2 under the condition of stirring, keeping the dropwise adding speed at 2 drops/second, adding all the rest solvent 2 after the dropwise adding, heating until the solvent is distilled off, stopping heating when the solid content of the system reaches 50% according to the calculated amount, and cooling to obtain an ethylene component and a hydroxyl-containing polymer;
(3) Preparation of UVB-resistant and wear-resistant polyurethane resin containing acrylic chain segments:
the prepared component A and component B are prepared according to the mass ratio of 2:1, standing, coating on an organic glass plate by adopting a flow coating process after bubbles disappear, transferring the organic glass plate to a constant temperature drying oven after the surface of the coating is dried, and baking at 80 ℃ for at least 5 hours to obtain the UVB-resistant and wear-resistant polyurethane resin containing acrylic chain segments.
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