CN115304761B - Polyester ether polyol for high-performance polyurethane waterproof coating and preparation method thereof - Google Patents
Polyester ether polyol for high-performance polyurethane waterproof coating and preparation method thereof Download PDFInfo
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- CN115304761B CN115304761B CN202210962055.5A CN202210962055A CN115304761B CN 115304761 B CN115304761 B CN 115304761B CN 202210962055 A CN202210962055 A CN 202210962055A CN 115304761 B CN115304761 B CN 115304761B
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- polyester ether
- polyol
- polyurethane waterproof
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- 229920005862 polyol Polymers 0.000 title claims abstract description 89
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 229920000728 polyester Polymers 0.000 title claims abstract description 55
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 50
- 239000004814 polyurethane Substances 0.000 title claims abstract description 50
- -1 ether polyol Chemical class 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000000576 coating method Methods 0.000 title abstract description 33
- 239000011248 coating agent Substances 0.000 title abstract description 32
- 229920000570 polyether Polymers 0.000 claims abstract description 59
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 57
- 150000003077 polyols Chemical class 0.000 claims abstract description 46
- 239000003973 paint Substances 0.000 claims abstract description 27
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 10
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 9
- 238000007599 discharging Methods 0.000 claims abstract description 8
- 238000009826 distribution Methods 0.000 claims abstract description 7
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052751 metal Inorganic materials 0.000 claims abstract description 5
- 239000002184 metal Substances 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 48
- 238000006243 chemical reaction Methods 0.000 claims description 47
- 239000000203 mixture Substances 0.000 claims description 45
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 32
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 3
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 3
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 2
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 claims description 2
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 claims description 2
- ZRMYHUFDVLRYPN-UHFFFAOYSA-N 3-oxabicyclo[3.1.0]hexane-2,4-dione Chemical compound O=C1OC(=O)C2CC12 ZRMYHUFDVLRYPN-UHFFFAOYSA-N 0.000 claims description 2
- NMSRALOLNIBERV-UHFFFAOYSA-N 4,5,6,6a-tetrahydro-3ah-cyclopenta[c]furan-1,3-dione Chemical compound C1CCC2C(=O)OC(=O)C21 NMSRALOLNIBERV-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229940014800 succinic anhydride Drugs 0.000 claims description 2
- 238000004220 aggregation Methods 0.000 claims 2
- 230000002776 aggregation Effects 0.000 claims 2
- 238000013329 compounding Methods 0.000 claims 1
- 230000007062 hydrolysis Effects 0.000 abstract description 7
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 7
- 238000013461 design Methods 0.000 abstract description 5
- 239000000047 product Substances 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 239000000178 monomer Substances 0.000 description 8
- 230000000977 initiatory effect Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 6
- 238000006467 substitution reaction Methods 0.000 description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 239000008199 coating composition Substances 0.000 description 4
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000001723 curing Methods 0.000 description 3
- 150000002009 diols Chemical class 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000004970 Chain extender Substances 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000013065 commercial product Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920005906 polyester polyol Polymers 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- HRELNAWNYHNHHO-UHFFFAOYSA-N bis(7-methyloctyl) benzene-1,2-dicarboxylate cyclohexane Chemical group C1CCCCC1.C(CCCCCC(C)C)OC(C=1C(C(=O)OCCCCCCC(C)C)=CC=CC1)=O HRELNAWNYHNHHO-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- FHCUBHNQRLFINC-UHFFFAOYSA-N dodecamagnesium hexasilicate Chemical compound [Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] FHCUBHNQRLFINC-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical group O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000013008 moisture curing Methods 0.000 description 1
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000009489 vacuum treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2615—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen the other compounds containing carboxylic acid, ester or anhydride 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
- C08G65/2645—Metals or compounds thereof, e.g. salts
- C08G65/2663—Metal cyanide catalysts, i.e. DMC's
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2696—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the process or apparatus used
-
- 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
- C09D175/08—Polyurethanes from 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
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
- C08G2650/58—Ethylene oxide or propylene oxide copolymers, e.g. pluronics
Abstract
The invention belongs to the technical field of polyether polyol, and particularly relates to polyester ether polyol for high-performance polyurethane waterproof paint and a preparation method thereof. The preparation method of the polyester ether polyol for the high-performance polyurethane waterproof coating adopts low-molecular-weight polyether polyol with functionality of 2 and 3 as a mixing head, and after the polyether polyol is compounded with anhydride, double-metal cyanide complex is used as a catalyst to carry out segmented polymerization with alkylene oxide, and finally 3-5 polyester ether polyols with equal molecular weight intervals and normal molecular weight distribution are obtained by adopting a segmented discharging mode. The polyester ether polyol disclosed by the invention adopts a special molecular structure design, and the prepared polyurethane waterproof coating has excellent hydrolysis resistance and mechanical strength, and simultaneously has better flexibility, low temperature resistance and higher bonding strength, so that the polyurethane waterproof coating has excellent performance.
Description
Technical Field
The invention belongs to the technical field of polyether polyol, and particularly relates to polyester ether polyol for high-performance polyurethane waterproof paint and a preparation method thereof.
Background
The polyurethane waterproof coating is a high-grade durable synthetic resin coating, has the advantages of excellent overall waterproof effect, light waterproof layer, high strength, good elasticity, strong binding power, high and low temperature resistance, corrosion resistance, easy repair and the like, and can be used for waterproof of projects such as building roofs, outer walls, basements, roads, bridges and the like.
The polyurethane waterproof paint comprises two main types of double-component polyurethane waterproof paint and single-component polyurethane waterproof paint. Compared with the double-component polyurethane waterproof coating, the single-component polyurethane waterproof coating does not need to be prepared on site when in use, is simpler and more convenient to construct, has excellent coating performance, has good waterproof and mechanical properties due to moderate viscosity of the prepolymer, does not need to be diluted by a solvent and has a urea bond structure generated after the prepolymer is solidified. However, because the single-component polyurethane waterproof coating adopts moisture curing in the film-forming curing process, the formed polyurethane material has less component content for forming a hard segment, and the mechanical property of the material is generally poorer than that of the double-component coating. In order to achieve better mechanical property indexes, various properties of the polyurethane waterproof coating can be improved by using high-quality main polyol. In a general polyurethane waterproof coating formula system, a plurality of polyether polyols are required to be compounded and used, and the polyether polyols with the molecular weight of 2000 in two functions and 5000 in three functions are usually used as main polyether polyols.
The polyol used in the polyurethane waterproof paint mainly comprises polyether type and polyester type. The polyester polyol contains ester groups, so that the synthesized polyurethane material has higher tensile strength, lower elongation, insufficient hydrolysis resistance and high price. The polyurethane material synthesized by polyether polyol has lower cohesive energy of ether bond, and the product is generally softer, higher in elongation, good in hydrolysis resistance and inferior in mechanical property as polyester.
Patent CN202110388487.5 discloses a preparation method of polyether polyol for high-performance waterproof paint, which uses a mixture of difunctional compound and trifunctional compound as initiator, uses alkali metal or DMC as catalyst, and makes polymerization reaction with alkylene oxide to obtain polyether polyol crude polymer; and refining the crude polymer to obtain the target polyether polyol. When the polyether polyol is applied to the polyurethane waterproof paint formula, the polyether polyol is used for replacing the traditional mixture of multiple polyethers, the viscosity of the paint can be reduced, and the performance of the polyurethane waterproof paint after film formation is improved.
Patent CN201410384281.5 discloses a synthetic method of polyether polyol for waterproof paint, which is prepared by adopting an alcohol compound and a physical medium to form a mixed initiator, polymerizing sodium methoxide and propylene oxide in the first stage under the conditions of 0-0.5Mpa and 50-150 ℃, polymerizing sodium hydride and ethylene oxide in the second stage, and finely treating with magnesium hexasilicate, aluminum silicate and an organic deodorant. The prepared polyether polyol has low potassium sodium ions, low odor and narrow molecular weight distribution, and the composite coating prepared based on the polyether polyol has the advantages of improving the performance of polyurethane spraying and coating, being environment-friendly and durable, and enhancing the competitiveness of the product. There is no case of using polyester ether polyol in the aspect of polyurethane waterproof coating.
Disclosure of Invention
The invention aims to solve the technical problems that: the polyester ether polyol for the high-performance polyurethane waterproof coating has excellent hydrolysis resistance and mechanical strength, and simultaneously has better flexibility, low temperature resistance and higher bonding strength, so that the polyurethane waterproof coating has excellent performance; the invention also provides a preparation method thereof, which is suitable for industrial mass production.
The invention relates to a preparation method of polyester ether polyol for high-performance polyurethane waterproof paint, which adopts low molecular weight polyether polyol with functionality of 2 and 3 as a mixing head, and after being compounded with anhydride, double metal cyanide complex is used as a catalyst to carry out segmented polymerization with alkylene oxide, and finally 3-5 polyester ether polyols with equal molecular weight intervals and normal distribution of mass are obtained by adopting a segmented discharging mode.
In the present invention, the low molecular weight polyether polyols having functionalities of 2 and 3 have a molecular weight of 300 to 1000.
The molar ratio of the low molecular weight polyether polyol with the functionality of 2 to the low molecular weight polyether polyol with the functionality of 3 is 9:1-1:1.
In the invention, the anhydride is one or more of maleic anhydride, phthalic anhydride, glutaric anhydride, succinic anhydride, citraconic anhydride, itaconic anhydride, 1, 2-cyclopentanedioic anhydride and cyclopropane-1, 2-dicarboxylic anhydride.
The mass ratio of the total mass of the low molecular weight polyether polyol to the anhydride is 1:0.5-1:20.
In the present invention, the amount of the double metal cyanide complex catalyst is 0.02 to 0.06wt% of the theoretical yield of the polyester ether polyol.
In the present invention, the sectional polymerization is preferably divided into two sections.
The alkylene oxide used in the first polymerization stage is propylene oxide, and the amount of the propylene oxide is 30-90 wt% of the theoretical yield of the polyester ether polyol.
The alkylene oxide used in the second-stage polymerization is a mixture of propylene oxide and ethylene oxide, the propylene oxide is used in an amount of 10-50 wt% of the theoretical yield of the polyester ether polyol, and the ethylene oxide is used in an amount of 1-30 wt% of the theoretical yield of the polyester ether polyol.
In the invention, the reaction temperature of the segmented polymerization is 120-160 ℃, preferably 135-145 ℃; the reaction time is 3-8 h. The reaction temperature is more favorable for ring-opening polymerization of polyether polyol, anhydride and propylene oxide.
When the segmented polymerization reaction is carried out, firstly, low molecular weight polyether polyol, anhydride and catalyst are added into a polymerization kettle, nitrogen is adopted for replacement until the oxygen content in the kettle is smaller than 50ppm, the kettle is vacuumized until the vacuum degree is minus 0.09-minus 0.093MPa, the temperature is raised to 120-160 ℃, and then alkylene oxide is introduced for the segmented polymerization reaction.
In the polyester ether polyol product obtained by adopting a segmented discharging mode, the molecular weight interval of each polyester ether polyol is 50-500, and the mass is normally distributed according to the proportion of 1:2:1-1:10:1 or 1:2:1-1:10:10:1 or 1:2:3:2:1-1:10:20:10:1.
The relaxation time of molecular chains can be increased by adopting a sectional discharging mode, and when the polyurethane waterproof coating is used for the polyurethane waterproof coating, the mechanical strength of the polyurethane waterproof coating can be improved, and the polyurethane waterproof coating with high elongation at break can be obtained.
As a preferable scheme, the preparation method of the polyester ether polyol for the high-performance polyurethane waterproof paint comprises the following steps:
adding the oligomer polyether polyol with the functionality of 2 and 3, anhydride and a catalyst into a pressure-resistant reaction kettle, mixing, replacing nitrogen to ensure that the oxygen content in the kettle is less than 50ppm, vacuumizing to-0.09 to-0.093 MPa, heating, adding propylene oxide for polymerization reaction, continuing internal pressure reaction for 1-1.5 h after the reaction is finished, adding a mixture of propylene oxide and ethylene oxide in sections according to molecular weight design, taking out sections into the same post-treatment kettle, vacuumizing for 0.5-1 h, and removing unreacted propylene oxide monomers and micromolecular byproducts to obtain the polyester ether polyol with equal molecular weight intervals and normal distribution of mass.
The polyester ether polyol for the high-performance polyurethane waterproof paint is prepared by the preparation method, has a number average molecular weight of 1500-4500, a functionality of 2.1-2.5, a hydroxyl value of 23-145mgKOH/g and a viscosity of 600-1500 mPa.s at 25 ℃.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention adopts a unique molecular structure design, and the polyester ether molecular structure prepared by adopting a bimetallic catalytic system contains both ether bonds and ester bonds, so that the prepared single-component polyurethane waterproof coating has the excellent performances of polyether and polyester, and has good flexibility, hydrolysis resistance and higher mechanical strength;
(2) The invention adopts a special discharging mode, designs a molecular weight distribution mode, increases the relaxation time of a molecular chain, adopts one polyether in a formula system of the polyurethane waterproof coating to replace two or more traditional polyethers, and improves the elongation at break and the tensile strength of the prepared single-component polyurethane waterproof coating by 20-50% compared with the traditional single-component polyurethane waterproof coating.
Detailed Description
The present invention will be further described with reference to examples, but the scope of the invention is not limited thereto, and modifications made by those skilled in the art to which the present invention pertains should be made.
The raw materials used in the examples, unless otherwise specified, were all commercially available conventional raw materials; the process used in the examples, unless otherwise specified, is conventional in the art.
Example 1
360g of C204 (2-functionality, 400-molecular-weight polyether polyol, sold by Novey New material Co., ltd.), 50g of C305 (3-functionality, 500-molecular-weight polyether polyol, sold by NoveWin New material Co., ltd.), 110g of phthalic anhydride, 0.93g of DMC, nitrogen substitution, after oxygen content in the autoclave is less than 50ppm, vacuumizing to-0.09-0.093 MPa, heating to 135 ℃, adding 41g of propylene oxide for initiating reaction, when the pressure in the autoclave is obviously reduced and the temperature is sharply increased, indicating that the catalyst is successfully induced and activated, continuously adding 1203g of propylene oxide for polymerization reaction, continuing the internal pressure reaction after the addition is finished for 0.5h, then adding 331g of a mixture of propylene oxide and 110g of ethylene oxide, removing the internal pressure reaction for 1h, continuing the addition of 63g of a mixture of propylene oxide and 3g of ethylene oxide, removing 1160g of the internal pressure reaction for 0.5h, then adding the mixture of ethylene oxide and the internal pressure reaction for 40g of ethylene oxide into the same autoclave, and removing the same target polyether after the internal pressure of 40g of ethylene oxide is continuously removed for 0.5h, and finally removing the polyether ether after the internal pressure of the same reaction is continuously added for 0.575 h.
The product has the functionality of 2.1, the number average molecular weight of 2300g/mol, the hydroxyl value of 51.5mgKOH/g, the viscosity of 922 mPa.s and the interval of 90 between the three molecular weights, and the mass ratio of 1:2:1.
Example 2
320g of C204 (2-functionality, 400-molecular-weight polyether polyol, sold by Novey New material Co., ltd.), 100g of C305 (3-functionality, 500-molecular-weight polyether polyol, sold by NoveWipe New material Co., ltd.), 175.7g of maleic anhydride, 1.04g of DMC, nitrogen substitution, after oxygen content in the autoclave is less than 50ppm, vacuumizing to-0.09-0.093 MPa, heating to 135 ℃, adding 42g of propylene oxide for initiating reaction, when the pressure in the autoclave is obviously reduced and the temperature is sharply increased, indicating that the catalyst is successfully induced and activated, continuously adding 1370g of propylene oxide for polymerization reaction, continuously adding 377g of propylene oxide and 125g of ethylene oxide mixture after the addition, continuously adding 520g of 60g of propylene oxide and 3g of ethylene oxide mixture after the internal pressure reaction is reacted for 1h into a post-treatment autoclave, continuously adding 1560g of propylene oxide and 2g of ethylene oxide mixture after the internal pressure reaction is carried out for 1560.5 h, continuously adding the mixture into the same autoclave after the internal pressure is reacted for 24g of ethylene oxide and continuously removing the same polyether monomer after the internal pressure is reacted for 2h, and continuously removing the polyester monomer after the internal pressure is completely reacted for 2 h.
The product has the functionality of 2.2, the number average molecular weight of 2590g/mol, the hydroxyl value of 48.0mgKOH/g, the viscosity of 895 mPa.s, the interval between the three molecular weights of 80 and the mass ratio of 1:3:1.
Example 3
280g of C204 (2-functionality, 400-molecular-weight polyether polyol, sold by Nov New material Co., ltd.), 150g of C305 (3-functionality, 500-molecular-weight polyether polyol, sold by Nov New material Co., ltd.), 257.5g of glutaric anhydride, 1.16g of DMC, nitrogen substitution, after oxygen content in the autoclave is less than 50ppm, vacuumizing to minus 0.09 to minus 0.093MPa, heating to 135 ℃, adding 43g of propylene oxide for initiating reaction, when the pressure in the autoclave is obviously reduced and the temperature is sharply increased, indicating that the catalyst is successfully induced and activated, continuously adding 1330g of propylene oxide for polymerization reaction, continuing the internal pressure reaction for 0.5h after the addition, then adding 386g of a mixture of propylene oxide and 129g of ethylene oxide, removing 666g of the mixture into a post-treatment autoclave after the internal pressure reaction for 1h, continuing to add 53g of the mixture of propylene oxide and 3g of ethylene oxide, removing 133 g of the mixture into the same post-treatment autoclave after the internal pressure reaction for 0.5h, adding 34g of the mixture of propylene oxide and the ethylene oxide into the same after the internal pressure reaction kettle for the internal pressure reaction for 2h, continuously removing the same polyether ether after the internal pressure reaction for 0.5h, and continuously removing the polyester monomer after the internal pressure of the mixture is completely and completely removing the same after the polyester monomer is subjected to the reaction is subjected to the target is removed.
The product has a functionality of 2.2, a number average molecular weight of 2650g/mol, a hydroxyl value of 47.4mgKOH/g, a viscosity of 877 mPa.s, a spacing of 70 between the three molecular weights and a mass ratio of 1:2:1.
Example 4
320g of C204 (2-functionality, 400-molecular polyether polyol, sold by Novey New material Co., ltd.), 100g of C305 (3-functionality, 500-molecular polyether polyol, sold by Novey New material Co., ltd.), 170g of maleic anhydride, 1.15g of DMC, nitrogen substitution, vacuum pumping to-0.09-0.093 MPa after oxygen content in the reactor is less than 50ppm, heating to 135 ℃, adding 42g of propylene oxide for initiating reaction, when the pressure in the reactor obviously drops and the temperature rises sharply, indicating that the catalyst is successfully activated by induction, controlling the temperature in the reactor to 140+/-2 ℃, continuously adding 1312g of propylene oxide for polymerization reaction, and continuing the internal pressure reaction for 0.5h after the material is added, then adding 365g of the mixture of propylene oxide and 121g of ethylene oxide, removing 440g of the mixture into a post-treatment kettle after the internal pressure reaction for 1h, continuously adding 62g of the mixture of propylene oxide and 3g of ethylene oxide, removing 880g of the mixture into the same post-treatment kettle after the internal pressure reaction for 0.5h, continuously adding 102g of the mixture of propylene oxide and 5g of ethylene oxide, removing 880g of the mixture into the same post-treatment kettle after the internal pressure reaction for 0.5h, continuously adding 35g of the mixture of propylene oxide and 2g of ethylene oxide, completely removing the mixture into the same post-treatment kettle after the internal pressure reaction for 0.5h, and vacuumizing to remove the monomer for 0.5h to obtain the target polyester ether polyol 4.
The product has the functionality of 2.2, the number average molecular weight of 2550g/mol, the hydroxyl value of 48.6mgKOH/g, the viscosity of 869 mPa.s and the interval between the four molecular weights of 80, and the mass ratio of 1:2:2:1.
Example 5
320g of C204 (2-functionality, 400-molecular polyether polyol, sold by Novey New material Co., ltd.), 100g of C305 (3-functionality, 500-molecular polyether polyol, sold by Novey New material Co., ltd.), 170g of maleic anhydride, 1.15g of DMC, nitrogen substitution, vacuum pumping to-0.09-0.093 MPa after oxygen content in the reaction kettle is less than 50ppm, heating to 135 ℃, adding 42g of propylene oxide for initiating reaction, when the pressure in the reaction kettle obviously decreases and the temperature sharply increases, indicating that the catalyst is successfully induced and activated, controlling the temperature in the reaction kettle to 140+/-2 ℃, continuously adding 1312g of propylene oxide for polymerization reaction, continuing the internal pressure reaction for 0.5h after the addition, then adding 365g of the mixture of propylene oxide and 121g of ethylene oxide, removing 312g of the mixture into a post-treatment kettle after internal pressure reaction for 1h, continuously adding 66g of the mixture of propylene oxide and 4g of ethylene oxide, removing 624g of the mixture into the same post-treatment kettle after internal pressure reaction for 0.5h, continuously adding 190g of the mixture of propylene oxide and 10g of ethylene oxide, removing 936g of the mixture into the same post-treatment kettle after internal pressure reaction for 0.5h, continuously adding 67g of the mixture of propylene oxide and 4g of ethylene oxide, removing 624g of the mixture into the same post-treatment kettle after internal pressure reaction for 0.5h, continuously adding 34g of the mixture of propylene oxide and 2g of ethylene oxide, completely removing the mixture into the same post-treatment kettle after internal pressure reaction for 0.5h, and vacuumizing to remove monomers for 0.5h to obtain the target polyester ether polyol 5.
The product has the functionality of 2.2, the number average molecular weight of 2590g/mol, the hydroxyl value of 47.8mgKOH/g, the viscosity of 890 mPa.s, the interval between the five molecular weights of 80 and the mass ratio of 1:2:3:2:1.
Comparative example 1
320g of C204 (2-functionality, 400-molecular-weight polyether polyol, sold by Novey New material Co., ltd.), 100g of C305 (3-functionality, 500-molecular-weight polyether polyol, sold by Novey New material Co., ltd.), 0.08g of DMC, nitrogen substitution, vacuum pumping to-0.09-0.093 MPa after the oxygen content in the autoclave is less than 50ppm, heating to 135 ℃, adding 42g of propylene oxide for initiating reaction, controlling the temperature 140+ -2 ℃ in the autoclave to continuously add 1546g of propylene oxide for polymerization reaction when the pressure in the autoclave is obviously reduced and the temperature is suddenly increased, continuing to add 377g of propylene oxide and 125g of ethylene oxide mixture after the addition, removing 520g of ethylene oxide mixture into the post-treatment autoclave after the internal pressure reaction for 1h, continuing to add 60g of propylene oxide and 3g of ethylene oxide mixture, removing 1560g into the same post-treatment autoclave after the internal pressure reaction for 0.5h, then adding 24g of propylene oxide and 2g of ethylene oxide mixture into the same post-treatment autoclave after the internal pressure reaction for 0.5h, and removing all the polyester ether after the internal pressure is continuously removed into the same autoclave for the vacuum treatment for 0.5h, thus obtaining the target polyester ether.
The product has a functionality of 2.2, a number average molecular weight of 2590g/mol, a hydroxyl value of 47.9mgKOH/g, a viscosity of 458 mPa.s, a spacing of 80 between the three molecular weights and a mass ratio of 1:3:1.
Comparative example 2
320g of C204 (2-functionality, 400-molecular-weight polyether polyol, sold by Nov New material Co., ltd.), 100g of C305 (3-functionality, 500-molecular-weight polyether polyol, sold by Nov New material Co., ltd.), 176g of maleic anhydride, 1.04g of DMC, replacing nitrogen, measuring the oxygen content in the reactor to be less than 50ppm, vacuumizing to-0.09-0.093 MPa, heating to 135 ℃, adding 42g of propylene oxide for initiating reaction, when the pressure in the reactor is obviously reduced and the temperature is rapidly increased, indicating that the catalyst is successfully induced and activated, continuously adding 1434g of propylene oxide for polymerization reaction at 140+/-2 ℃, continuing the internal pressure reaction for 0.5h after the addition, then adding 389g of a mixture of propylene oxide and 129g of ethylene oxide for 1h, vacuumizing for removing monomers for 0.5h, and obtaining the target polyester ether polyol B.
The product has a functionality of 2.2, a number average molecular weight of 2590g/mol, a hydroxyl value of 48.4mgKOH/g and a viscosity of 887 mPa.s.
Examples 6 to 10 and comparative examples 3 to 6
The polyester ether polyols prepared in examples 1-5 and comparative examples 1-2 were used in water-resistant coatings with the raw material compositions shown in Table 1 in parts by weight. Wherein the waterproof coating formulations of examples 6-10 correspond to the polyester ether polyols prepared in examples 1-5, respectively, and the waterproof coating formulations of comparative examples 3-4 correspond to the polyester ether polyols prepared in comparative examples 1-2, respectively, and the formulations of comparative examples 5-6 do not contain polyester ether polyol.
The polyether triol is commercially available from INOVOL F330N, new material, mono, shandong.
The polyether glycol is INOVOL C220, a product sold by New material Co., ltd.
The polyester diol adopts POL-156, which is commercially available from Qingdao Xinyutian chemical industry Co.
TDI was toluene diisocyanate (TDI-80), a commercially available product from Shandong Jimmy macroisocyanate Co., ltd.
The chain extender adopts an amine aliphatic chain extender and is a product sold in the air chemical industry in the United states.
The silane coupling agent adopts KH550 and is commercially available from Shandong Zibo Kabushiki Kaisha.
The filler is kaolin, heavy calcium carbonate powder or a mixture of light calcium carbonate powder, and is commercially available from Tianjin chemical reagent Co., ltd.
The plasticizer is cyclohexane 1, 2-diisononyl phthalate, which is commercially available from Basff, germany.
The latent curing agent is WHA-208, which is a commercial product of Yao Yuwei company, inc. of Taiyuan, shanxi.
The catalyst adopts dibutyl tin dilaurate (DBTDL), which is a commercial product of national medicine group chemical reagent Co.
The preparation method of the waterproof coating comprises the following steps:
putting polyester ether polyol (or polyether triol/polyester diol/polyether triol/polyether diol), plasticizer and filler into a reaction kettle, dispersing uniformly at high speed, vacuumizing to-0.093 MPa, heating to 110 ℃ and dehydrating for 3 hours. Sampling and detecting moisture, cooling to 60 ℃ after the moisture is qualified, adding metered TDI, slowly heating to 80 ℃ for reaction for 2 hours, sampling and testing NCO content, adding 150# solvent oil when the NCO content reaches or approaches a theoretical value, continuing to react for 1 hour, cooling to 70 ℃, adding a latent curing agent and a catalyst, stirring and reacting for 0.5 hour, cooling to below 60 ℃, discharging, and sealing with nitrogen gas to obtain the single-component polyurethane waterproof coating.
The single-component polyurethane waterproof paint prepared in examples 6-10 and comparative examples 3-6 are uniformly mixed, uniformly coated on a mold coated with a release agent by a scraping plate, and the coating is finished for 2-3 times, so that the thickness of the final coating film is 1.5mm, and the final coating film is maintained for 7d under standard test conditions of (23+/-2) DEG C and relative humidity (50+/-5)%, and the performance of the coating film is detected according to the method of the standard GB/T19250-2013 polyurethane waterproof paint. The results of the performance test are shown in Table 1.
TABLE 1 waterproof coating formulations and Performance test results for examples 6-10 and comparative examples 3-6
From the results of the performance test in Table 1, it is understood that the one-component polyurethane waterproof paint obtained in each example has better tensile strength, tear strength, elongation at break and hydrolysis resistance than the product obtained in the comparative example under the same conditions. The polyester ether polyol prepared by the invention combines the excellent properties of the polyester polyol and the polyether polyol, has higher mechanical strength and better hydrolysis resistance than the waterproof paint synthesized by polyester or polyether, and simultaneously designs the molecular weight distribution mode of the polyester ether polyol, so as to increase the relaxation time of molecular chains, be used in the polyurethane waterproof paint, improve the mechanical strength of the polyurethane waterproof paint and obtain the polyurethane waterproof paint with high elongation at break.
Claims (6)
1. A preparation method of polyester ether polyol for polyurethane waterproof paint is characterized in that: adopting low molecular weight polyether polyol with functionality of 2 and 3 as a mixing head, compounding with anhydride, using double metal cyanide complex as a catalyst, carrying out segmented polymerization with alkylene oxide, and finally adopting a segmented discharging mode to obtain 3-5 polyester ether polyols with equal molecular weight intervals and normal distribution of mass;
the molecular weight of the low molecular weight polyether polyol with the functionality of 2 and 3 is 300-1000;
the molar ratio of the low molecular weight polyether polyol with the functionality of 2 to the low molecular weight polyether polyol with the functionality of 3 is 9:1-1:1;
the mass ratio of the total mass of the low molecular weight polyether polyol to the anhydride is 1:0.5-1:20;
in the polyester ether polyol product obtained by adopting the segmented discharging mode, the molecular weight interval of each polyester ether polyol is 50-500, and the mass is normally distributed according to the proportion of 1:2:1-1:10:1 or 1:2:1-1:10:10:1 or 1:2:3:2:1-1:10:20:10:1.
2. The method for producing a polyester ether polyol for a polyurethane waterproof paint according to claim 1, characterized in that: the anhydride is one or more of maleic anhydride, phthalic anhydride, glutaric anhydride, succinic anhydride, citraconic anhydride, itaconic anhydride, 1, 2-cyclopentanedioic anhydride and cyclopropane-1, 2-dicarboxylic anhydride.
3. The method for producing a polyester ether polyol for a polyurethane waterproof paint according to claim 1, characterized in that: the dosage of the double metal cyanide complex catalyst is 0.02-0.06 wt% of the theoretical yield of the polyester ether polyol.
4. The method for producing a polyester ether polyol for a polyurethane waterproof paint according to claim 1, characterized in that: the sectional aggregation is two-section aggregation;
the alkylene oxide adopted in the first-stage polymerization is propylene oxide, and the amount of the propylene oxide is 30-90 wt% of the theoretical yield of the polyester ether polyol;
the alkylene oxide used in the second-stage polymerization is a mixture of propylene oxide and ethylene oxide, the amount of the propylene oxide is 10-50wt% of the theoretical yield of the polyester ether polyol, and the amount of the ethylene oxide is 1-30wt% of the theoretical yield of the polyester ether polyol.
5. The method for producing a polyester ether polyol for a polyurethane waterproof paint according to claim 1, characterized in that: the reaction temperature of the segmented polymerization is 120-160 ℃, and the reaction time is 3-8 h.
6. A polyester ether polyol for polyurethane waterproof paint is characterized in that: the polymer composition prepared by the preparation method according to any one of claims 1 to 5, wherein the number average molecular weight is 1500-4500, the functionality is 2.1-2.5, the hydroxyl value is 23-145mgKOH/g, and the viscosity at 25 ℃ is 600-1500 mPas.
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