CN115304761A - 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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- CN115304761A CN115304761A CN202210962055.5A CN202210962055A CN115304761A CN 115304761 A CN115304761 A CN 115304761A CN 202210962055 A CN202210962055 A CN 202210962055A CN 115304761 A CN115304761 A CN 115304761A
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- Prior art keywords
- polyester ether
- waterproof coating
- polyurethane waterproof
- ether polyol
- polyol
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- 229920005862 polyol Polymers 0.000 title claims abstract description 94
- 229920000728 polyester Polymers 0.000 title claims abstract description 64
- 238000000576 coating method Methods 0.000 title claims abstract description 59
- 239000011248 coating agent Substances 0.000 title claims abstract description 58
- 239000004814 polyurethane Substances 0.000 title claims abstract description 54
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 54
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims abstract description 47
- -1 ether polyol Chemical class 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229920000570 polyether Polymers 0.000 claims abstract description 62
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 60
- 150000003077 polyols Chemical class 0.000 claims abstract description 51
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 25
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 9
- 238000007599 discharging Methods 0.000 claims abstract description 8
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 6
- 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 5
- 238000013329 compounding Methods 0.000 claims abstract 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 54
- 238000006243 chemical reaction Methods 0.000 claims description 48
- 239000000203 mixture Substances 0.000 claims description 35
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 12
- 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
- 150000008065 acid anhydrides Chemical class 0.000 claims description 5
- 238000009826 distribution 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
- 230000008569 process Effects 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
- 239000003973 paint Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229940014800 succinic anhydride Drugs 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 abstract description 7
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 7
- 239000000047 product Substances 0.000 description 34
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 239000000178 monomer Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 8
- 230000000977 initiatory effect Effects 0.000 description 7
- 230000004913 activation Effects 0.000 description 5
- 239000008199 coating composition Substances 0.000 description 5
- 230000006698 induction Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- 150000002009 diols Chemical class 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
- 238000011056 performance test Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004970 Chain extender Substances 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
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 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
- 229920000642 polymer Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000007858 starting material 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
- 238000004078 waterproofing Methods 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 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
- 150000001298 alcohols Chemical class 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
- 230000001588 bifunctional effect Effects 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
- 239000013065 commercial product Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- 238000001514 detection method Methods 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
- 229940079593 drug Drugs 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
- 238000009472 formulation Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 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
- 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
- 238000003756 stirring Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 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
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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
- C09D175/08—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
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Polyethers (AREA)
Abstract
The invention belongs to the technical field of polyether polyol, and particularly relates to polyester polyether polyol for a high-performance polyurethane waterproof coating and a preparation method thereof. The preparation method of the polyester ether polyol for the high-performance polyurethane waterproof coating comprises the steps of adopting low-molecular-weight polyether polyols with the functionality degrees of 2 and 3 as a mixing stub bar, compounding the low-molecular-weight polyether polyols with anhydride, then carrying out segmented polymerization with alkylene oxide by adopting a double metal cyanide complex as a catalyst, and finally obtaining 3-5 polyester ether polyols with the same molecular weight interval and normally distributed molecular weights by adopting a segmented discharging mode. The polyester ether polyol is designed by adopting a special molecular structure, 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 polyether polyol for a high-performance polyurethane waterproof coating 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 bonding force, high and low temperature resistance, corrosion resistance, easiness in repair and the like, and can be used for waterproofing of projects such as building roofs, external walls, basements, roads, bridges and the like.
The polyurethane waterproof coating comprises two major types of double-component polyurethane waterproof coating and single-component polyurethane waterproof coating. Compared with a bi-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, and has good waterproof and mechanical properties because the viscosity of the prepolymer is moderate and does not need to be diluted by a solvent, and a urea bond structure generated after the prepolymer is cured. However, because the single-component polyurethane waterproof coating is cured by moisture in the film-forming and curing process, the content of the components forming the hard segment in the formed polyurethane material is less, and the mechanical property of the material is generally poorer than that of the two-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 body polyol. A general polyurethane waterproof coating formula system needs multiple polyether polyols to be compounded for use, and the polyether polyols with difunctional 2000 molecular weight and trifunctional 5000 molecular weight are mainly used.
The polyols used in the polyurethane waterproof coating mainly comprise polyether type and polyester type. Because polyester polyol contains ester group, the synthesized polyurethane material has higher tensile strength, lower elongation, insufficient hydrolysis resistance and high price. The polyurethane material synthesized by polyether polyol has the advantages of generally softer product, higher elongation, good hydrolysis resistance and inferior mechanical property to polyester type because of lower cohesive energy of ether bond.
Patent CN202110388487.5 discloses a preparation method of polyether polyol for high-performance waterproof coating, which takes a mixture of a bifunctional compound and a trifunctional compound as an initiator, takes alkali metal or DMC as a catalyst, and carries out polymerization reaction with alkylene oxide to prepare a polyether polyol crude polymer; and refining the crude polymer to obtain the target polyether polyol. When the polyether polyol is applied to a polyurethane waterproof coating formula, one polyether polyol is used for replacing traditional mixing of various polyethers, the viscosity of the coating can be reduced, and the performance of the polyurethane waterproof coating after film forming is improved.
Patent CN201410384281.5 discloses a synthesis method of polyether polyol for waterproof coating, which adopts alcohol compounds and physical media to form a mixed initiator, and under the conditions of 0-0.5Mpa and 50-150 ℃, sodium methoxide and propylene oxide are polymerized in the first stage, sodium hydride and ethylene oxide are polymerized in the second stage, and magnesium hexasilicate, aluminum silicate and organic deodorant are used for fine treatment to obtain the polyether polyol. The prepared polyether polyol has low potassium and sodium ions, low odor and narrow molecular weight distribution, and the combined coating prepared on the basis of the polyether polyol has the advantages of improving the performances of sprayed polyurethane and coating, mainly protecting environment and being durable, and enhancing the competitiveness of the product. At present, no use case of the polyester ether polyol is seen in the aspect of polyurethane waterproof coating.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the polyester ether polyol for the high-performance polyurethane waterproof coating is provided, and the prepared polyurethane waterproof coating has excellent hydrolysis resistance and mechanical strength by adopting a special molecular structure design, and has good flexibility, low temperature resistance and high bonding strength so as to have excellent performance; the invention also provides a preparation method of the compound, which is suitable for industrial mass production.
The preparation method of the polyester ether polyol for the high-performance polyurethane waterproof coating adopts low-molecular-weight polyether polyol with the functionality of 2 and 3 as a mixing stub bar, compounds the polyether polyol with anhydride, then carries out sectional polymerization with alkylene oxide by taking a double-metal cyanide complex as a catalyst, and finally obtains 3-5 types of polyester ether polyol with the same molecular weight interval and normally distributed mass by adopting a sectional discharging mode.
In the present invention, the low molecular weight polyether polyols having functionalities of 2 and 3 have molecular weights 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 acid 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 acid anhydride is 1.
In the invention, the dosage of the double metal cyanide complex catalyst is 0.02-0.06 wt% of the theoretical yield of the polyester ether polyol.
In the present invention, the segmented polymerization is preferably divided into two-stage polymerization.
The alkylene oxide adopted in the first-stage polymerization is propylene oxide, and the dosage of the propylene oxide is 30-90 wt% of the theoretical yield of the polyester ether polyol.
The alkylene oxide adopted by the second-stage polymerization is a mixture of propylene oxide and ethylene oxide, the dosage of the propylene oxide is 10-50 wt% of the theoretical yield of the polyester ether polyol, and the dosage of the ethylene oxide is 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 ring-opening polymerization of polyether polyol, anhydride and propylene oxide is more facilitated at the reaction temperature.
During the sectional polymerization reaction, firstly adding the low molecular weight polyether polyol, the anhydride and the catalyst into a polymerization kettle, adopting nitrogen to replace the low molecular weight polyether polyol, the anhydride and the catalyst until the oxygen content in the kettle is less than 50ppm, vacuumizing the kettle until the vacuum degree is-0.09 to-0.093 MPa, heating the kettle to 120 to 160 ℃, and then introducing the alkylene oxide to carry out the sectional polymerization reaction.
In the invention, in the polyester ether polyol product obtained by adopting a sectional discharging mode, the molecular weight interval of each polyester ether polyol is 50-500, and the mass ratio of 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, so that the polyurethane waterproof coating with high elongation at break is obtained.
As a preferable scheme, the preparation method of the polyester ether polyol for the high-performance polyurethane waterproof coating comprises the following steps:
adding oligomer polyether polyol with the functionality of 2 and 3, acid anhydride and a catalyst into a pressure-resistant reaction kettle, mixing, replacing with 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, continuing to perform 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 the molecular weight design, moving the mixture out of the same post-treatment kettle in sections, vacuumizing for 0.5-1 h, and removing unreacted propylene oxide monomers and micromolecular byproducts to obtain the polyester polyether polyol with the same molecular weight interval and normal mass distribution.
The polyester ether polyol for the high-performance polyurethane waterproof coating is prepared by the preparation method, 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 mPa & s.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention adopts unique molecular structure design, and the polyester ether molecular structure prepared by adopting a bimetallic catalytic system contains ether bond and ester bond, so that the prepared single-component polyurethane waterproof coating has the excellent performances of both 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 molecular chains, adopts one polyether in a formula system of the polyurethane waterproof coating to replace two or more conventional polyethers, and can improve the breaking elongation and the tensile strength of the prepared single-component polyurethane waterproof coating by 20-50 percent compared with the conventional single-component polyurethane waterproof coating.
Detailed Description
The present invention is further illustrated by the following examples, but the scope of the present invention is not limited thereto, and modifications of the technical solutions of the present invention by those skilled in the art should be within the scope of the present invention.
The starting materials used in the examples are, unless otherwise specified, commercially available conventional starting materials; the processes used in the examples are, unless otherwise specified, conventional in the art.
Example 1
360g of C204 (polyether polyol with the molecular weight of 2 and 400, a product sold by Nowey New Material Co., ltd.), 50g of C305 (polyether polyol with the molecular weight of 3 and 500, a product sold by Nowey New Material Co., ltd.), 110g of phthalic anhydride and 0.93g of DMC are added into a pressure-resistant reaction kettle, nitrogen is replaced, after the oxygen content in the kettle is measured to be less than 50ppm, the vacuum is pumped to-0.09 to-0.093 MPa, the temperature is increased to 135 ℃, 41g of propylene oxide is added for initiating reaction, when the pressure in the reaction kettle is obviously reduced and the temperature is sharply increased, the successful induction and activation of the catalyst is indicated, controlling the temperature in the kettle to be 140 +/-2 ℃, continuously adding 1203g of propylene oxide for polymerization reaction, continuously carrying out internal pressure reaction for 0.5h after the feeding is finished, then adding a mixture of 331g of propylene oxide and 110g of ethylene oxide, removing 575g of propylene oxide into a post-treatment kettle after 1h of internal pressure reaction, continuously adding a mixture of 63g of propylene oxide and 3g of ethylene oxide, removing 1160g of propylene oxide into the same post-treatment kettle after 0.5h of internal pressure reaction, then continuously adding a mixture of 40g of propylene oxide and 2g of ethylene oxide, completely removing the mixture into the same post-treatment kettle after 0.5h of internal pressure reaction, vacuumizing and removing monomers for 0.5h to obtain the target polyester ether polyol 1.
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, the interval between the three molecular weights is 90, and the mass ratio is 1.
Example 2
320g of C204 (polyether polyol with 2 functionality and 400 molecular weight, a product sold by Nowey New Material Co., ltd.), 100g of C305 (polyether polyol with 3 functionality and 500 molecular weight, a product sold by Nowey New Material Co., ltd.), 175.7g of maleic anhydride, 1.04g of DMC are added into a pressure-resistant reaction kettle, nitrogen replacement is carried out, after the oxygen content in the kettle is measured to be less than 50ppm, the vacuum is carried out to-0.09 to-0.093 MPa, the temperature is increased to 135 ℃, 42g of propylene oxide is added for initiating reaction, when the pressure in the reaction kettle is obviously reduced and the temperature is sharply increased, the catalyst is successfully induced and activated, the temperature in the kettle is controlled to be 140 +/-2 ℃, 1370g of propylene oxide is continuously added for polymerization reaction, after the internal pressure reaction is finished, the internal pressure reaction is continuously carried out for 0.5h, then 377g of propylene oxide and 125g of ethylene oxide mixture are added, 520g of the internal pressure reaction is carried out for 1h, then the mixture of 520g of propylene oxide is removed into a post-treatment kettle, 60g of propylene oxide and the mixture of 3g of ethylene oxide is continuously added into the same post-treatment kettle, the polyester monomer is removed after 1560.5 h, and the polyester monomer is completely removed, the target monomer is obtained after the polyester is removed.
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 is 80, and the mass ratio is 1.
Example 3
280g of C204 (polyether polyol with the molecular weight of 2 and 400, a product sold by Nowey New Material Co., ltd.), 150g of C305 (polyether polyol with the molecular weight of 3 and 500, a product sold by Nowey New Material Co., ltd.), 257.5g of glutaric anhydride, 1.16g of DMC are added into a pressure-resistant reaction kettle, nitrogen is replaced, after the oxygen content in the kettle is measured to be less than 50ppm, the pressure is vacuumized to-0.09 to-0.093 MPa, the temperature is increased to 135 ℃, 43g of propylene oxide is added for initiating reaction, when the pressure in the reaction kettle is obviously reduced and the temperature is sharply increased, the catalyst is successfully induced and activated, the temperature in the kettle is controlled to be 140 +/-2 ℃, 1330g of propylene oxide is continuously added for polymerization, the internal pressure reaction is continued for 0.5h after the feeding is finished, 386g of a mixture of propylene oxide and 129g of ethylene oxide is then added, the mixture of propylene oxide and 129g of ethylene oxide are removed after the internal pressure reaction is carried out for 1h, 666g of the post-treatment kettle, 53g of the mixture of propylene oxide and 3g of ethylene oxide are continuously added into the post-treatment kettle, the mixture of polyester and the polyester monomer is removed after the internal pressure is carried out for 0.5h, the target treatment, the reaction kettle, the target reaction is obtained.
The product has the functionality of 2.2, the number average molecular weight of 2650g/mol, the hydroxyl value of 47.4mgKOH/g, the viscosity of 877 mPa.s, the interval between the three molecular weights is 70, and the mass ratio is 1.
Example 4
Adding 320g of C204 (polyether polyol with 2 functionality and 400 molecular weight, a product sold by Nowey New Material Co., ltd.), 100g of C305 (polyether polyol with 3 functionality and 500 molecular weight, a product sold by Nowey New Material Co., ltd.), 170g of maleic anhydride, 1.15g of DMC, replacing nitrogen, measuring the oxygen content in the autoclave 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 autoclave is obviously reduced and the temperature is sharply increased, indicating that the induction and activation of the catalyst are successful, controlling the temperature in the autoclave to be 140 +/-2 ℃, continuously adding 1312g of propylene oxide for polymerization, continuing internal pressure reaction for 0.5h after feeding is finished, then adding 365g of propylene oxide and 121g of ethylene oxide mixture, moving out a post-treatment autoclave after internal pressure reaction for 1h, continuously adding 62g of propylene oxide and 3g of ethylene oxide mixture, moving out of the same post-treatment autoclave after internal pressure reaction for 0.5h, moving out of the same post-treatment autoclave for 1h, continuously adding 102g of propylene oxide and moving out of polyester mixture of the same post-treatment autoclave for 2.5 h, and removing the same monomer mixture after vacuum, obtaining polyester mixture after all the target monomer is removed.
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, the interval between the four molecular weights is 80, and the mass ratio is 1.
Example 5
Adding 320g of C204 (polyether glycol with the molecular weight of 2 and 400, a product sold by Nowev New Material Co., ltd.), 100g of C305 (polyether glycol with the molecular weight of 3 and 500, a product sold by Nowev New Material Co., ltd.), 170g of maleic anhydride, 1.15g of DMC into a pressure-resistant reaction kettle, replacing nitrogen, measuring the oxygen content in the kettle to be less than 50ppm, vacuumizing to-0.09 to-0.093 MPa, heating to 135 ℃, adding 42g of propylene oxide for initiating reaction, when the pressure in the reaction kettle is obviously reduced and the temperature is rapidly increased, indicating that the induction and activation of the catalyst are successful, controlling the temperature in the kettle to be 140 +/-2 ℃, continuously adding 1312g of propylene oxide for polymerization reaction, continuously carrying out internal pressure reaction for 0.5h after the feeding is finished, and adding a mixture of 365g of propylene oxide and 121g of ethylene oxide, reacting for 1 hour under internal pressure, removing 312g of propylene oxide into a post-treatment kettle, continuously adding a mixture of 66g of propylene oxide and 4g of ethylene oxide, reacting for 0.5 hour under internal pressure, removing 624g of ethylene oxide into the same post-treatment kettle, continuously adding a mixture of 190g of propylene oxide and 10g of ethylene oxide, reacting for 0.5 hour under internal pressure, removing 936g of propylene oxide into the same post-treatment kettle, continuously adding a mixture of 67g of propylene oxide and 4g of ethylene oxide, reacting for 0.5 hour under internal pressure, removing 624g of propylene oxide into the same post-treatment kettle, continuously adding a mixture of 34g of propylene oxide and 2g of ethylene oxide, reacting for 0.5 hour under internal pressure, completely removing into the same post-treatment kettle, and vacuumizing for 0.5 hour 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 five molecular weights of 80, and the mass ratio of 1.
Comparative example 1
320g of C204 (polyether polyol with 2 functionality and 400 molecular weight, a product sold by Nowey New Material Co., ltd.), 100g of C305 (polyether polyol with 3 functionality and 500 molecular weight, a product sold by Nowey New Material Co., ltd.), 0.08g of DMC, nitrogen replacement, when the oxygen content in the pressure-resistant reaction kettle is measured 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 reaction kettle is obviously reduced and the temperature is sharply increased, indicating that the induction and activation of the catalyst are successful, controlling the temperature in the kettle to be 140 +/-2 ℃, continuously adding 1546g of propylene oxide for polymerization reaction, continuously carrying out internal pressure reaction for 0.5h after the feeding is finished, then adding 377g of a mixture of propylene oxide and 125g of ethylene oxide, continuously adding 24g of a mixture of propylene oxide and 2g of ethylene oxide for 1h, removing 520g of propylene oxide into a post-treatment kettle, continuously adding 60g of a mixture of propylene oxide and 3g of ethylene oxide, continuously removing 1560.5 h after internal pressure reaction for 0.5h, removing the mixture of polyester monomer into the same post-treatment kettle, and removing the polyester monomer A to obtain the target product.
The product has the functionality of 2.2, the number average molecular weight of 2590g/mol, the hydroxyl value of 47.9mgKOH/g, the viscosity of 458 mPa.s, the interval between the three molecular weights is 80, and the mass ratio is 1.
Comparative example 2
Adding 320g of C204 (polyether polyol with the molecular weight of 2 and 400, a product sold by Nowev New Material Co., ltd.), 100g of C305 (polyether polyol with the molecular weight of 3 and 500, a product sold by Nowev New Material Co., ltd.), 176g of maleic anhydride and 1.04g of DMC into a pressure-resistant reaction kettle, replacing nitrogen, measuring the oxygen content in the kettle 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 reaction kettle is obviously reduced and the temperature is rapidly increased, indicating that the induction and activation of the catalyst are successful, controlling the temperature in the kettle to be 140 +/-2 ℃, continuously adding 1434g of propylene oxide for polymerization reaction, continuing to perform internal pressure reaction for 0.5h after the feeding is finished, then adding 389g of a mixture of propylene oxide and 129g of ethylene oxide, performing internal pressure reaction for 1h, vacuumizing and removing monomers for 0.5h to obtain the target polyester polyether polyol B.
The product has the functionality of 2.2, the number average molecular weight of 2590g/mol, the hydroxyl value of 48.4mgKOH/g and the viscosity of 887 mPas.
Examples 6 to 10 and comparative examples 3 to 6
The polyester ether polyols prepared in examples 1 to 5 and comparative examples 1 to 2 were used in a waterproof coating material, and the raw material composition thereof was as 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, 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 polyols.
The polyether triol is available from INOVOL F330N, new Norway Shandong, inc.
The polyether diol was obtained from INOVOL C220, a commercially available product of Shandong-Nowei New Material Co.
The polyester diol is POL-156, a product sold by Qingdao Xinyutian chemical industry Co.
TDI was toluene diisocyanate (TDI-80), a product commercially available from Shandong Taiwan isocyanate Ltd.
The chain extender adopts amine aliphatic chain extender and is a product sold in American air chemical industry.
The silane coupling agent is KH550 which is a product sold in Shandong Zibo Kangdao chemical industry Co.
The filler is a mixture of kaolin, heavy calcium carbonate powder or light calcium carbonate powder, and is a product sold by Tianjin Kemiou chemical reagent company Limited.
Cyclohexane 1,2-diisononyl dicarboxylate, a commercial product of basf, germany, was used as the plasticizer.
The latent curing agent is a product sold by WHA-208, taiyuan Yao Yuwei, shanxi, and the like.
The catalyst adopts dibutyltin dilaurate (DBTDL) which is a product sold by national drug group chemical reagent company Limited.
The preparation method of the waterproof coating comprises the following steps:
putting polyester ether polyol (or polyether triol/polyester diol/polyether triol/polyether diol), a plasticizer and filler into a reaction kettle, dispersing uniformly at a high speed, vacuumizing to-0.093 MPa, heating to 110 ℃, and dehydrating for 3 hours. Sampling to detect moisture, cooling to 60 ℃ after the moisture is qualified, adding measured TDI, slowly heating to 80 ℃ for reaction for 2 hours, sampling to test the NCO content, adding 150# solvent oil when the NCO content reaches or approaches to a theoretical value, continuing the reaction for 1 hour, cooling to 70 ℃, adding a latent curing agent and a catalyst, stirring for reaction for 0.5 hour, cooling to below 60 ℃, discharging, and sealing with nitrogen to obtain the single-component polyurethane waterproof coating.
The single-component polyurethane waterproof coatings prepared in examples 6 to 10 and comparative examples 3 to 6 are respectively and uniformly mixed, uniformly coated on a mold coated with a release agent by a scraper, coated for 2 to 3 times to obtain a final coating film with the thickness of 1.5mm, maintained for 7 days under the standard test conditions of (23 +/-2) DEG C and relative humidity (50 +/-5)% and subjected to coating film performance detection according to the method of the standard GB/T19250-2013 polyurethane waterproof coating. The results of the performance tests are shown in table 1.
TABLE 1 waterproof coating formulations and Performance test results of examples 6-10 and comparative examples 3-6
According to the results of the performance tests in table 1, it can be seen that the one-component polyurethane waterproofing 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 integrates the excellent performances of polyester polyol and polyether polyol, has higher mechanical strength and better hydrolysis resistance than a waterproof coating synthesized by only using polyester or polyether, and simultaneously, the molecular weight distribution mode of the polyester ether polyol is designed to increase the relaxation time of a molecular chain, so that the polyester ether polyol is used in the polyurethane waterproof coating, the mechanical strength of the polyurethane waterproof coating is improved, and the polyurethane waterproof coating with high elongation at break is obtained.
Claims (10)
1. A preparation method of polyester ether polyol for high-performance polyurethane waterproof paint is characterized by comprising the following steps: taking low molecular weight polyether polyols with the functionality degrees of 2 and 3 as a mixing stub bar, compounding the mixture with anhydride, taking a double metal cyanide complex as a catalyst, carrying out sectional polymerization with alkylene oxide, and finally obtaining 3-5 polyester polyether polyols with the same molecular weight interval and normal mass distribution by adopting a sectional discharging mode.
2. The method for preparing polyester ether polyol for high-performance polyurethane waterproof coating according to claim 1, characterized in that: the low molecular weight polyether polyols having functionalities of 2 and 3 have molecular weights of 300 to 1000.
3. The method for preparing polyester ether polyol for high-performance polyurethane waterproof coating according to claim 1, characterized in that: 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.
4. The method for preparing polyester ether polyol for high-performance polyurethane waterproof coating according to claim 1, characterized in that: the acid anhydride is one or more of maleic anhydride, phthalic anhydride, glutaric anhydride, succinic anhydride, citraconic anhydride, itaconic anhydride, 1,2-cyclopentanedioic anhydride, cyclopropane-1,2-dicarboxylic anhydride.
5. The method for preparing polyester ether polyol for high-performance polyurethane waterproof coating according to claim 1, characterized in that: the mass ratio of the total mass of the low molecular weight polyether polyol to the acid anhydride is 1.
6. The method for preparing polyester ether polyol for high-performance polyurethane waterproof coating 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 output of the polyester ether polyol.
7. The method for preparing polyester ether polyol for high-performance polyurethane waterproof coating according to claim 1, characterized in that: the segmented polymerization is preferably divided into two-segment polymerization;
the alkylene oxide adopted in the first-stage polymerization is propylene oxide, and the dosage of the propylene oxide is 30-90 wt% of the theoretical yield of the polyester ether polyol.
The alkylene oxide adopted by the second-stage polymerization is a mixture of propylene oxide and ethylene oxide, the dosage of the propylene oxide is 10-50 wt% of the theoretical yield of the polyester ether polyol, and the dosage of the ethylene oxide is 1-30 wt% of the theoretical yield of the polyester ether polyol.
8. The method for preparing polyester ether polyol for high-performance polyurethane waterproof coating according to claim 1, characterized in that: the reaction temperature of the sectional polymerization is 120-160 ℃, and the reaction time is 3-8 h.
9. The method for preparing polyester ether polyol for high-performance polyurethane waterproof coating according to claim 1, characterized in that: in the polyester ether polyol product obtained by adopting a staged discharging mode, the molecular weight interval of each polyester ether polyol is 50-500, and the mass ratio is in a ratio of 1.
10. The polyester ether polyol for the high-performance polyurethane waterproof coating is characterized by comprising the following components in percentage by weight: prepared by the process according to any one of claims 1 to 9, having a number average molecular weight of from 1500 to 4500, a functionality of from 2.1 to 2.5, a hydroxyl number of from 23 to 145mgKOH/g and a viscosity of from 600 to 1500 mPas at 25 ℃.
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