CN117777395A - Isocyanate-terminated elastomer resin, preparation method thereof, coating component and application - Google Patents
Isocyanate-terminated elastomer resin, preparation method thereof, coating component and application Download PDFInfo
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- CN117777395A CN117777395A CN202311806871.8A CN202311806871A CN117777395A CN 117777395 A CN117777395 A CN 117777395A CN 202311806871 A CN202311806871 A CN 202311806871A CN 117777395 A CN117777395 A CN 117777395A
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- 239000000806 elastomer Substances 0.000 title claims abstract description 58
- 239000011347 resin Substances 0.000 title claims abstract description 45
- 229920005989 resin Polymers 0.000 title claims abstract description 45
- 238000000576 coating method Methods 0.000 title claims abstract description 37
- 239000011248 coating agent Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 229920000642 polymer Polymers 0.000 claims abstract description 26
- 229920000728 polyester Polymers 0.000 claims abstract description 25
- 239000000178 monomer Substances 0.000 claims abstract description 20
- 239000002253 acid Substances 0.000 claims abstract description 18
- 239000012948 isocyanate Substances 0.000 claims abstract description 18
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 17
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 17
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 239000012975 dibutyltin dilaurate Substances 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 239000000047 product Substances 0.000 claims abstract description 16
- -1 hydroxyl polyol Chemical class 0.000 claims abstract description 15
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 229920005862 polyol Polymers 0.000 claims abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims description 24
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 11
- 239000008199 coating composition Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 150000002009 diols Chemical class 0.000 claims description 8
- 238000007259 addition reaction Methods 0.000 claims description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 6
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 4
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 claims description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 3
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 claims description 3
- 239000001361 adipic acid Substances 0.000 claims description 3
- 235000011037 adipic acid Nutrition 0.000 claims description 3
- BVFSYZFXJYAPQJ-UHFFFAOYSA-N butyl(oxo)tin Chemical group CCCC[Sn]=O BVFSYZFXJYAPQJ-UHFFFAOYSA-N 0.000 claims description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 3
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- 239000002184 metal Substances 0.000 claims description 3
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 3
- 239000001384 succinic acid Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 7
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- 229920003225 polyurethane elastomer Polymers 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
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- 229920000515 polycarbonate Polymers 0.000 description 4
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- 238000010992 reflux Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- 230000003628 erosive effect Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
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- 241001391944 Commicarpus scandens Species 0.000 description 2
- 208000005156 Dehydration Diseases 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000011527 polyurethane coating Substances 0.000 description 2
- 238000009418 renovation Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229920002121 Hydroxyl-terminated polybutadiene Polymers 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
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- 238000003860 storage Methods 0.000 description 1
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- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical compound NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 description 1
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- Polyurethanes Or Polyureas (AREA)
Abstract
The invention belongs to the technical field of coatings, and particularly relates to an isocyanate-terminated elastomer resin, a preparation method thereof, a coating component and application thereof. The preparation method of the isocyanate-terminated elastomer resin comprises the following steps: heating dihydric alcohol, dibasic acid and a catalyst to perform polycondensation reaction, wherein the acid value of a polycondensation reaction product is less than or equal to 5mgKOH/g, and obtaining a polyester solution; mixing the polyester solution with hydroxyl-terminated fluorosilicone polymer to obtain polyester-fluorosilicone mixture solution; the polyester-fluorosilicone mixture solution is mixed with dibutyl tin dilaurate, diisocyanate monomer is added dropwise, and when the free isocyanate radical content in the product reaches the designed value, the isocyanate terminated elastomer resin is obtained. The coating prepared by the reaction of the isocyanate-terminated elastomer resin and the hydroxyl polyol elastomer has excellent ultralow temperature resistance, excellent hydrophobicity and ultraviolet light resistance, and can be applied to places with ultralow temperature, weather resistance and steam corrosion resistance.
Description
Technical Field
The invention relates to the technical field of coatings, in particular to isocyanate-terminated elastomer resin, a preparation method thereof, a coating component and application thereof.
Background
The adhesion characteristics of the polyurethane coating materials on weather resistance or different materials are more involved, however, various extremely cold protection states are often encountered in life, in which state, if small workpieces can be obtained by means of continuous renovation or replacement, and the outdoor large structural parts are required to be supported with high cost for replacement or renovation, which can cause great difficulty in the practical application process. In particular, the protection of materials in ultra-low temperature storage or delivery conditions, and the protective coating of elastic paint is an effective way of resisting low temperature fatigue.
At present, polyurethane elastomers basically adopt isocyanate to chain extend dihydric alcohol, most of the related dihydric alcohol is polyester or polyether, the acid and alkali resistance of the polyester is slightly poor, the low-temperature crystallinity is obvious, and the application of the polyurethane elastomer in an ultralow-temperature environment is limited. Polyethers have advantages over polyesters in terms of film formation integrity at low temperatures because of their low temperature crystallinity, but polyethers are subject to uv damage in outdoor applications and become a bottleneck.
The volatile polyurethane elastomer is difficult to dissolve when applied as a coating due to the excessive molecular weight of the material, and the coating is too thin, so that the construction cost is greatly increased; meanwhile, the coating has very limited protection due to the linear structure. Currently, outdoor polyurethane elastomer plastics mainly appear in allophanate modified polyurethane elastomer (CN 200780004521.2), hydrogenated hydroxyl-terminated polybutadiene (application chemistry 34 (10): 1110,2007) and polycarbonate diol (CN 201880081792.6), but are basically not of practical significance in outdoor material protection as polyurethane elastomer plastics, but can be inspired as an elastomer preparation method. In terms of coating applications, the reaction of isocyanate-terminated elastomers with hydroxyl polyols is favored for outdoor applications, and isocyanate-terminated polyurethane elastomers are currently marketed primarily as adducts of polycarbonates or polyester polyols, such as E3380N (polycarbonate adduct, common coating chemical company, in the state), desmodur N3800 (adducts of fatty amines, phenols, anhydrides) by scion, for outdoor durability. The two elastic isocyanate crosslinking agents are easy to crystallize in a low-temperature state due to the adoption of groups such as polycarbonate, aliphatic amine, phenolic aldehyde, anhydride and the like, when the application environment temperature is too low, the coating is easy to be in a glass state in the crystallization state, and the coating is easy to break along with the alternating change of ultralow temperature and room temperature, so that the coating loses protection significance.
Disclosure of Invention
The invention aims at overcoming the defect that an elastic isocyanate cross-linking agent in the prior art is mostly an addition product of groups which are easy to crystallize at a low temperature, so that a polyurethane coating prepared by the elastic isocyanate cross-linking agent is easy to break at a lower temperature, and further provides an isocyanate-terminated elastomer resin, a preparation method thereof, a coating component and application thereof. The isocyanate-terminated elastomer resin is prepared by performing polycondensation reaction on dihydric alcohol and dibasic acid under the action of a catalyst to generate a polyester solution with hydroxyl ends, then mixing the polyester solution with hydroxyl ends with a hydroxyl-terminated fluorosilicone polymer, adding a diisocyanate monomer and dibutyltin dilaurate into the mixed solution, and performing addition reaction on the diisocyanate monomer by the polyester solution (polyester dihydric alcohol oligomer) and the hydroxyl-terminated fluorosilicone polymer under the catalysis of dibutyltin dilaurate, so as to chain-extend the diisocyanate monomer to obtain the isocyanate-terminated elastomer resin. The coating prepared by the reaction of the isocyanate-terminated elastomer resin and the hydroxyl polyol elastomer is not affected by the integrity and hydrophobicity of the coating under the condition of alternating circulation of liquid nitrogen and liquid hydrogen in use environment and room temperature, the ultralow temperature protection performance of the coating is effectively embodied, and the coating also has excellent hydrophobicity and ultraviolet light resistance, and can be applied to places with extremely low temperature, weather resistance and steam erosion resistance.
In order to realize the material protection in the outdoor ultralow temperature environment, the isocyanate-terminated elastomer and the polyisocyanate elastomer are crosslinked, so that the method is a convenient and low-cost effective mode for protecting the outdoor material. The invention uses low-polarity low-branching degree as the addition product chain extender of the isocyanate from the standpoint of effectively reducing the crystallinity of the blocked isocyanate at low temperature, thereby effectively promoting the cold resistance of the coating film after the polyurethane is crosslinked.
The first aspect of the present invention provides a method for producing an isocyanate-terminated elastomer resin, comprising the steps of:
(1) Mixing dihydric alcohol, dibasic acid, a catalyst and dimethylbenzene, heating to 220-230 ℃ for polycondensation reaction, cooling to 50-60 ℃ when the acid value of a polycondensation reaction product is less than or equal to 5mgKOH/g, and adding dimethylbenzene into the polycondensation reaction product to obtain a polyester solution with terminal hydroxyl groups, wherein the hydroxyl value of the polyester solution is 1.8-2.2%;
(2) Mixing the polyester solution in the step (1) with hydroxyl-terminated fluorosilicone polymer to obtain a polyester-fluorosilicone mixture solution;
(3) And (3) mixing the polyester-fluorosilicone mixture solution in the step (2) with dibutyltin dilaurate, heating to 50-60 ℃, starting to dropwise add diisocyanate monomers for addition reaction, continuously preserving heat for 50-70 min after the dropwise adding is finished, starting to measure the free isocyanate content in the product, cooling to room temperature when the free isocyanate content in the product reaches a designed value, and filtering to obtain the isocyanate-terminated elastomer resin.
Preferably, the hydroxyl-terminated fluorosilicone polymer is a linear polymer of the structure shown in formula (1),
wherein n is an integer between 30 and 100, and the viscosity of the hydroxyl-terminated fluorosilicone polymer is 5000-30000 cp.
Preferably, the diisocyanate monomer is an aliphatic diisocyanate monomer. More preferably, the diisocyanate monomer is selected from one or more than two of isophorone diisocyanate, hexamethylene diisocyanate, and 4,4' -dicyclohexylmethane diisocyanate.
Preferably, the isocyanate-terminated elastomer resin contains a hydroxyl-terminated fluorosilicone polymer, and the hydroxyl-terminated fluorosilicone polymer has a mass number of 5 to 10% based on 100% of the total mass of the isocyanate-terminated elastomer resin.
Preferably, in step (1), the catalyst is monobutyl tin oxide.
Preferably, in the step (1), the mass number of the catalyst is 0.05 to 0.06% based on 100% of the total mass of the diol, the dibasic acid and the catalyst.
Preferably, in step (1), the slow temperature increase is performed under stirring conditions, and the process is as follows: when the temperature is 100-160 ℃, the stirring speed is 80-120 rpm; when the temperature is more than 160 ℃, the stirring speed is 6-8 m/min.
Preferably, the dihydric alcohol is selected from one or more of 2-methyl-1, 3-propanediol, 1, 4-cyclohexanedimethanol, 1, 6-hexanediol and neopentyl glycol.
Preferably, the dibasic acid is adipic acid and/or succinic acid.
The second aspect of the present invention provides an isocyanate-terminated elastomer resin prepared by the method described above.
In a third aspect, the present invention provides a coating composition comprising the isocyanate-terminated elastomeric resin described above, a hydroxyl polyol elastomer, and dibutyltin dilaurate.
According to a fourth aspect of the present invention, there is provided an application of a coating composition, wherein the isocyanate-terminated elastomer resin and the hydroxyl polyol elastomer are mixed according to NCO/oh=1.0 to 1.1 to obtain a mixture, and then dibutyl tin dilaurate with a mass number of 0.5 to 1% is added into the mixture, and finally the obtained coating material is coated on a metal surface.
In the isocyanate-terminated elastomer resin and the preparation method, the coating component and the application thereof, the isocyanate-terminated elastomer resin has the following beneficial effects:
(1) In the invention, firstly, a polyester diol solution with hydroxyl ends is generated by polycondensation reaction of diol and diacid under the action of a catalyst, then the polyester diol solution with hydroxyl ends is mixed with hydroxyl-terminated fluorosilicone polymer, and finally diisocyanate monomer and dibutyltin dilaurate are added into the mixed solution, and under the catalysis of dibutyltin dilaurate, the polyester diol solution and the hydroxyl-terminated fluorosilicone polymer carry out addition reaction on the diisocyanate monomer, so that the diisocyanate monomer is chain-extended to obtain isocyanate-terminated elastomer resin, and the free isocyanate content in the isocyanate-terminated elastomer resin is 5-12%;
(2) In the invention, the coating prepared by the reaction of the isocyanate-terminated elastomer resin and the hydroxyl polyol elastomer is not affected by the integrity and hydrophobicity of the coating under the condition of alternating circulation of the use environment of liquid nitrogen and liquid hydrogen and room temperature, the ultralow temperature protection performance of the coating is effectively embodied, and the coating also has excellent hydrophobicity and ultraviolet light resistance, and can be applied to places with extremely low temperature, weather resistance and steam erosion resistance.
Detailed Description
The following describes specific embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
The first aspect of the present invention provides a method for producing an isocyanate-terminated elastomer resin, comprising the steps of:
(1) Mixing dihydric alcohol, dibasic acid, a catalyst and dimethylbenzene, slowly heating to 220-230 ℃ to perform polycondensation reaction, cooling to 50-60 ℃ when the acid value of a polycondensation reaction product is less than or equal to 5mgKOH/g, and adding dimethylbenzene into the polycondensation reaction product to obtain a polyester solution with terminal hydroxyl groups, wherein the hydroxyl value of the polyester solution is 1.8-2.2%;
(2) Mixing the polyester solution in the step (1) with hydroxyl-terminated fluorosilicone polymer to obtain a polyester-fluorosilicone mixture solution;
(3) And (2) adding dibutyl tin dilaurate into the polyester-fluorosilicone mixture solution in the step (2), mixing, heating to 50-60 ℃, beginning to dropwise add diisocyanate monomer for addition reaction, continuing to keep the temperature for 50-70 min after the dropwise adding is finished, beginning to measure the free isocyanate content in the product, determining the design value according to the finally-expected performance of the isocyanate-terminated elastomer resin when the free isocyanate content in the product reaches the design value, and cooling to room temperature and filtering when the design value reaches 5-12% of the total mass of the product under the preferable condition to obtain the isocyanate-terminated elastomer resin.
In a specific embodiment of the method of the present invention, the reactions of steps (1) to (3) are all carried out in a reactor with stirring, heating, reflux dehydration apparatus, dropping funnel.
In a specific embodiment of the method of the present invention, the glycol is selected from one or more of 2-methyl-1, 3-propanediol, 1, 4-cyclohexanedimethanol, 1, 6-hexanediol and neopentyl glycol.
In the method of the invention, in a specific embodiment, the dibasic acid is adipic acid and/or succinic acid.
In a specific embodiment of the method of the present invention, in step (1), the catalyst is monobutyl tin oxide.
In the method of the present invention, in a specific embodiment, in the step (1), the mass number of the catalyst is 0.05 to 0.06%, for example, may be 0.05% or 0.06%, based on 100% of the total mass of the diol, the diacid and the catalyst.
In the method of the present invention, in a specific embodiment, in step (1), the xylene is used as a reflux solvent, and a dehydration treatment is required in advance. The amount of the xylene to be added is appropriately added according to the reaction process as long as the reflux can be promoted.
In the method of the present invention, in a specific embodiment, in step (1), the slow temperature increase is performed under stirring, and the process is as follows: when the temperature is 100-160 ℃, the stirring speed is 80-120 rpm; when the temperature is more than 160 ℃, the stirring speed is 6-8 m/min; when the temperature reaches 200 ℃, the temperature rising rate is 1 ℃/min and the temperature rises to 220-230 ℃.
In the method of the invention, in the preferred embodiment, in the step (1), tetrahydrophthalic anhydride can be added in the process of preparing the polyester solution, so that the finally prepared fluorosilicone-polyester-acrylic ester elastomer resin has certain toughness and is more beneficial to processing.
In a specific embodiment of the method of the present invention, in step (2), the hydroxyl-terminated fluorosilicone polymer is a linear polymer having a structure represented by formula (1),
wherein n is an integer between 30 and 100, and the viscosity of the hydroxyl-terminated fluorosilicone polymer is 5000-30000 cp. The hydroxyl-terminated fluorosilicone polymer has a main chain of a-Si-O-Si-structure, and a side chain of a fluorine-containing alkyl and methyl, so that the low surface tension of the polymer after film formation is ensured, the hydrophobic property of the coating is realized, the corrosion resistance of the coating to corrosive media is improved, and the influence of ultraviolet light on the stability of a molecular structure is reduced
In the method of the present invention, in a preferred embodiment, the isocyanate-terminated elastomer resin contains a hydroxyl-terminated fluorosilicone polymer (nonvolatile) in an amount of 5 to 10% by mass based on 100% by mass of the total isocyanate-terminated elastomer resin.
In a specific embodiment of the method of the present invention, in step (3), the diisocyanate monomer is an aliphatic diisocyanate monomer. More preferably, the diisocyanate monomer is selected from one or more than two of isophorone diisocyanate, hexamethylene diisocyanate, and 4,4' -dicyclohexylmethane diisocyanate.
The second aspect of the present invention provides an isocyanate-terminated elastomer resin prepared by the method described above.
In a preferred embodiment, the free isocyanate content of the isocyanate-terminated elastomer resin is from 5 to 12%
In a third aspect, the present invention provides a coating composition comprising the isocyanate-terminated elastomeric resin described above, a hydroxyl polyol elastomer, and dibutyltin dilaurate.
According to a fourth aspect of the present invention, there is provided an application of a coating composition, wherein the isocyanate-terminated elastomer resin and the hydroxyl polyol elastomer are mixed according to NCO/oh=1.0 to 1.1 to obtain a mixture, and then dibutyl tin dilaurate with a mass number of 0.5 to 1% is added into the mixture, and finally the obtained coating material is coated on a metal surface.
In a preferred embodiment, the hydroxyl polyol elastomer is elastic SS-1050, available from Jiangsu Ten New Material technology Co., ltd.
The isocyanate-terminated elastomer resin according to the present invention, the preparation method, the coating composition and the application thereof are further described below by way of examples. The embodiment is implemented on the premise of the technical scheme of the invention, and detailed implementation modes and specific operation processes are given, but the protection scope of the invention is not limited to the following embodiment.
The reagents in the examples below were obtained as usual on the market unless otherwise specified.
Hydroxyl-terminated fluorosilicone polymers: the manufacturer: viscosity of Shanghai silicon mountain Polymer Material Co., ltd.): 5000-30000cp;
organosilicon surface auxiliary agent: the manufacturer: pick, germany, product brand: byk3700;
hydroxyl polyol elastomer: the manufacturer: jiangsu Ten pine New Material technologies Co., ltd., product brand: elastic SS-1050.
The preparation of the isocyanate-terminated elastomer resins of examples 1-5 were all carried out as follows:
(1) Adding dihydric alcohol, dibasic acid, a catalyst and dimethylbenzene into a reactor with a stirring, heating, refluxing and dehydrating device and a dropping funnel, slowly starting stirring, starting heating, increasing the stirring speed to 100rpm when the temperature is increased to more than 100 ℃, increasing the stirring speed to 7m/min when the temperature is increased to more than 160 ℃, keeping the stirring speed constant all the time, pre-dehydrating the reactor for 30min, continuously dehydrating according to the heating speed of 1 ℃/min to 225 ℃, starting acid value measurement after 5h, ending dehydrating when the acid value of a polycondensation reaction product is less than or equal to 5mgKOH/g, cooling to 60 ℃, and adding dimethylbenzene into the polycondensation reaction product to obtain a polyester solution, wherein the hydroxyl value of the polyester solution is 2%;
(2) Stirring and mixing the polyester solution in the step (1) and the hydroxyl-terminated fluorosilicone polymer for 10min to obtain a mixed solution;
(3) And (3) mixing the mixed solution in the step (2) with dibutyltin dilaurate, then dropwise adding diisocyanate monomers into the obtained mixed product at 55 ℃ for addition reaction, continuously preserving heat for 60 minutes after the dropwise adding is finished, starting to measure the free isocyanate content in the product, cooling to room temperature when the free isocyanate content in the product reaches 5-12% of the total mass of the product, and filtering to obtain the isocyanate-terminated elastomer resin.
The raw material components of examples 1 to 5 are shown in Table 1
TABLE 1
Application example
The isocyanate-terminated elastomer resin prepared in examples 1 to 5 was weighed and mixed with the hydroxyl polyol elastomer according to NCO/oh=1.1 to obtain a mixture, 98.5% of the mixture obtained in examples 1 to 5 was weighed and added with 0.5% of dibutyltin dilaurate and 1% of an organosilicon surface auxiliary agent (byk 3700) to obtain a coating composition, and finally the coating material was coated on the surface of stainless steel to obtain a coating film, and the characteristic physicochemical parameters of the film after one week are shown in table 2:
TABLE 2
From the data in table 2, it can be seen that the coating prepared by the reaction of the isocyanate-terminated elastomer resin and the hydroxyl polyol elastomer of the invention has the advantages that the integrity and the hydrophobicity of the coating are not affected under the condition of alternating circulation of the use environment of liquid nitrogen and liquid hydrogen and room temperature, the ultralow temperature protection performance of the coating is effectively reflected, and the coating has excellent hydrophobicity and ultraviolet light resistance, and can be applied to places with extremely low temperature, weather resistance and steam erosion resistance.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (10)
1. A process for preparing an isocyanate-terminated elastomeric resin, comprising the steps of:
(1) Mixing dihydric alcohol, dibasic acid, a catalyst and dimethylbenzene, heating to 220-230 ℃ for polycondensation reaction, cooling to 50-60 ℃ when the acid value of a polycondensation reaction product is less than or equal to 5mgKOH/g, and adding dimethylbenzene into the polycondensation reaction product to obtain a polyester solution with terminal hydroxyl groups, wherein the hydroxyl value of the polyester solution is 1.8-2.2%;
(2) Mixing the polyester solution in the step (1) with hydroxyl-terminated fluorosilicone polymer to obtain a polyester-fluorosilicone mixture solution;
(3) And (3) adding dibutyl tin dilaurate into the polyester-fluorosilicone mixture solution in the step (2), mixing, heating to 50-60 ℃, beginning to dropwise add diisocyanate monomers for addition reaction, continuing to keep the temperature for 50-70 min after the dropwise adding is finished, beginning to measure the free isocyanate content in the product, cooling to room temperature when the free isocyanate content in the product reaches a designed value, and filtering to obtain the isocyanate-terminated elastomer resin.
2. The process according to claim 1, wherein the hydroxyl-terminated fluorosilicone polymer is a linear polymer having a structure represented by the formula (1),
wherein n is an integer between 30 and 100, and the viscosity of the hydroxyl-terminated fluorosilicone polymer is 5000-30000 cp.
3. The production method according to claim 1 or 2, wherein the diisocyanate monomer is an aliphatic diisocyanate monomer; and/or
The diisocyanate monomer is selected from one or more than two of isophorone diisocyanate, hexamethylene diisocyanate and 4,4' -dicyclohexylmethane diisocyanate.
4. The production method according to claim 2, wherein the isocyanate-terminated elastomer resin contains a hydroxyl-terminated fluorosilicone polymer, and the hydroxyl-terminated fluorosilicone polymer is present in an amount of 5 to 10% by mass based on 100% by mass of the total isocyanate-terminated elastomer resin.
5. The method of claim 1, wherein in step (1), the catalyst is monobutyl tin oxide; and/or
In the step (1), the mass number of the catalyst is 0.05-0.06% based on 100% of the total mass of the dihydric alcohol, the dibasic acid and the catalyst.
6. The method according to claim 1, wherein in the step (1), the temperature is raised under stirring, which is as follows: when the temperature is 100-160 ℃, the stirring speed is 80-120 rpm; when the temperature is more than 160 ℃, the stirring speed is 6-8 m/min.
7. The method according to claim 1, wherein the diol is one or more selected from the group consisting of 2-methyl-1, 3-propanediol, 1, 4-cyclohexanedimethanol, 1, 6-hexanediol and neopentyl glycol; and/or
The dibasic acid is adipic acid and/or succinic acid.
8. An isocyanate-terminated elastomer resin prepared by the process of any one of claims 1 to 7.
9. A coating composition comprising the isocyanate-terminated elastomeric resin of claim 8, a hydroxyl polyol elastomer, and dibutyltin dilaurate.
10. Use of a coating composition according to claim 9, characterized in that the isocyanate-terminated elastomer resin is first mixed with the hydroxyl polyol elastomer according to NCO/OH = 1.0-1.1 to obtain a mixture, and then dibutyl tin dilaurate with a mass number of 0.5-1% is added to the mixture for uniform mixing, and finally the obtained coating material is applied on the metal surface.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311806871.8A CN117777395A (en) | 2023-12-26 | 2023-12-26 | Isocyanate-terminated elastomer resin, preparation method thereof, coating component and application |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311806871.8A CN117777395A (en) | 2023-12-26 | 2023-12-26 | Isocyanate-terminated elastomer resin, preparation method thereof, coating component and application |
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| CN117777395A true CN117777395A (en) | 2024-03-29 |
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| CN202311806871.8A Pending CN117777395A (en) | 2023-12-26 | 2023-12-26 | Isocyanate-terminated elastomer resin, preparation method thereof, coating component and application |
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| CN (1) | CN117777395A (en) |
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- 2023-12-26 CN CN202311806871.8A patent/CN117777395A/en active Pending
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