CN114369236A - High-performance polyester ether polyol and preparation method and application thereof - Google Patents
High-performance polyester ether polyol and preparation method and application thereof Download PDFInfo
- Publication number
- CN114369236A CN114369236A CN202111441635.1A CN202111441635A CN114369236A CN 114369236 A CN114369236 A CN 114369236A CN 202111441635 A CN202111441635 A CN 202111441635A CN 114369236 A CN114369236 A CN 114369236A
- Authority
- CN
- China
- Prior art keywords
- polyester ether
- polyol
- reaction
- anhydride
- propylene oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920005862 polyol Polymers 0.000 title claims abstract description 86
- 229920000728 polyester Polymers 0.000 title claims abstract description 49
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims abstract description 39
- -1 ether polyol Chemical class 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000004917 polyol method Methods 0.000 title description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 58
- 229920000570 polyether Polymers 0.000 claims abstract description 58
- 150000003077 polyols Chemical class 0.000 claims abstract description 51
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000008065 acid anhydrides Chemical class 0.000 claims abstract description 7
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 6
- JCTXKRPTIMZBJT-UHFFFAOYSA-N 2,2,4-trimethylpentane-1,3-diol Chemical compound CC(C)C(O)C(C)(C)CO JCTXKRPTIMZBJT-UHFFFAOYSA-N 0.000 claims abstract description 4
- DSKYSDCYIODJPC-UHFFFAOYSA-N 2-butyl-2-ethylpropane-1,3-diol Chemical compound CCCCC(CC)(CO)CO DSKYSDCYIODJPC-UHFFFAOYSA-N 0.000 claims abstract description 4
- SXFJDZNJHVPHPH-UHFFFAOYSA-N 3-methylpentane-1,5-diol Chemical compound OCCC(C)CCO SXFJDZNJHVPHPH-UHFFFAOYSA-N 0.000 claims abstract description 4
- OJRJDENLRJHEJO-UHFFFAOYSA-N 2,4-diethylpentane-1,5-diol Chemical compound CCC(CO)CC(CC)CO OJRJDENLRJHEJO-UHFFFAOYSA-N 0.000 claims abstract description 3
- 230000000379 polymerizing effect Effects 0.000 claims abstract 4
- 238000006243 chemical reaction Methods 0.000 claims description 58
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 38
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 38
- 239000003054 catalyst Substances 0.000 claims description 25
- 238000006116 polymerization reaction Methods 0.000 claims description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims description 19
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 16
- 239000000178 monomer Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 239000000047 product Substances 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 9
- 230000018044 dehydration Effects 0.000 claims description 8
- 238000006297 dehydration reaction Methods 0.000 claims description 8
- 230000000977 initiatory effect Effects 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims description 6
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 6
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 claims description 4
- 150000008064 anhydrides Chemical class 0.000 claims description 4
- 239000006227 byproduct Substances 0.000 claims description 4
- 230000000694 effects 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
- 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
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 238000006386 neutralization reaction Methods 0.000 claims description 2
- 239000003973 paint Substances 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 claims description 2
- 229940014800 succinic anhydride Drugs 0.000 claims description 2
- 238000000576 coating method Methods 0.000 abstract description 37
- 239000011248 coating agent Substances 0.000 abstract description 35
- 229920002635 polyurethane Polymers 0.000 abstract description 29
- 239000004814 polyurethane Substances 0.000 abstract description 29
- 230000007062 hydrolysis Effects 0.000 abstract description 10
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 10
- 238000013461 design Methods 0.000 abstract description 3
- 239000003999 initiator Substances 0.000 abstract description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 17
- 239000000463 material Substances 0.000 description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 14
- 239000001301 oxygen Substances 0.000 description 14
- 229910052760 oxygen Inorganic materials 0.000 description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 230000008569 process Effects 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000001816 cooling Methods 0.000 description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 6
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 6
- 239000000391 magnesium silicate Substances 0.000 description 6
- 229910052919 magnesium silicate Inorganic materials 0.000 description 6
- 235000019792 magnesium silicate Nutrition 0.000 description 6
- 238000005086 pumping Methods 0.000 description 6
- 238000000967 suction filtration Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 4
- 150000002009 diols Chemical class 0.000 description 4
- 238000004078 waterproofing Methods 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 239000008199 coating composition Substances 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 229920005906 polyester polyol Polymers 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004970 Chain extender Substances 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-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
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 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
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 238000012653 anionic ring-opening polymerization Methods 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- HORIEOQXBKUKGQ-UHFFFAOYSA-N bis(7-methyloctyl) cyclohexane-1,2-dicarboxylate Chemical compound CC(C)CCCCCCOC(=O)C1CCCCC1C(=O)OCCCCCCC(C)C HORIEOQXBKUKGQ-UHFFFAOYSA-N 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
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000009776 industrial production Methods 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
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000036314 physical performance Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000004162 soil erosion Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000009182 swimming Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000002562 thickening agent 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
- C08G65/2606—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 containing hydroxyl groups
- C08G65/2609—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 containing hydroxyl groups containing aliphatic hydroxyl groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/6795—Unsaturated 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
- 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
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
- C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
- C08G65/3322—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof acyclic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- 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
- C08G2150/00—Compositions for coatings
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Polyethers (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to a high-performance polyester ether polyol and a preparation method and application thereof. The high-performance polyester ether polyol is obtained by polymerizing dihydric alcohol with a side group with alkylene oxide to obtain intermediate refined polyether polyol, mixing the intermediate refined polyether polyol with acid anhydride, and polymerizing the mixture with the alkylene oxide; the dihydric alcohol with the side group is one or more of 2,2, 4-trimethyl-1, 3-pentanediol, 2, 4-diethyl-1, 5-pentanediol, 2-butyl-2-ethyl-1, 3-propanediol and 3-methyl-1, 5-pentanediol. The invention adopts unique initiator and designs different molecular structures, and 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.
Description
Technical Field
The invention belongs to the technical field of polyether polyol, and particularly relates to high-performance polyester ether polyol and a preparation method and application thereof.
Background
The polyurethane waterproof coating is a high-grade durable synthetic resin coating, has the advantages of excellent integral waterproof effect, light waterproof layer, high strength, good elasticity, strong cohesive force, high and low temperature resistance, corrosion resistance, easy repair and the like, and can be used for waterproofing of building roofs, outer walls, basements, kitchens and bathrooms, water storage pools, swimming pools, roof gardens, subways, concrete member expansion joints, roads, bridges and other projects. 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 mono-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 the 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.
The polyols used in the polyurethane waterproof coating mainly comprise polyether type and polyester type. The polyester polyol contains ester group, so that the synthesized polyurethane material has high tensile strength, low elongation, good weather resistance, excellent physical performance and thermal stability, but insufficient hydrolysis resistance and high price. The polyurethane material synthesized by polyether polyol is generally softer and has higher elongation rate due to lower cohesive energy of ether bond; meanwhile, the hydrolysis resistance of ether bond is better than that of ester group, but the mechanical property of polyether polyurethane material is not as good as that of polyester type.
Patent CN201811467843.7 discloses a waterproof coating for building waterproofing and a preparation method thereof, in the preparation process, polyether polyol and polyester polyol are mixed, the waterproof coating for building waterproofing has better flexibility, low temperature resistance and higher bonding strength, but the formula system is a two-component polyurethane waterproof coating, the A component is polyether polyol, polyester polyol and isocyanate, and the B component is defoaming agent, curing agent, modified nano calcium carbonate filler, silane coupling agent modified nano silicon dioxide, thickening agent, dispersing agent and water.
The patent CN201410350004.2 discloses a hydrophilic single-component water-curing polyurethane and a preparation method thereof, wherein an anionic ring-opening polymerization means is adopted, polyethylene glycol is taken as initial dihydric alcohol, and is subjected to ring-opening polymerization with propylene oxide in the presence of KOH, and polyols with different molecular weights and hydrophilic and hydrophobic chain segment lengths are synthesized by adjusting the molecular weight of the polyethylene glycol, the addition amount of the polyethylene glycol and the addition amount of the propylene oxide; reacting polyol with isocyanate under the action of a catalyst, and adding a proper amount of plasticizer, antioxidant and ultraviolet absorbent to prepare a polyurethane prepolymer with an end group of-NCO; and mixing the prepolymer with water in a certain proportion to obtain the single-component water-cured polyurethane. The product obtained by the invention has high solid content, high curing speed, high water retention capacity, good storage stability, good flexibility, weather resistance and acid and alkali resistance, and has wide application prospects in the aspects of treating soil erosion and water loss, preparing waterproof materials and the like. 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 defects of the prior art are overcome, and the high-performance polyester ether polyol is provided, and has excellent performance by adopting a special initiator and a molecular structure design; the invention also provides a preparation method thereof, which is suitable for industrial mass production; and the single-component polyurethane waterproof coating is applied to preparation of single-component polyurethane waterproof coating, has excellent hydrolysis resistance and mechanical strength, and simultaneously has good flexibility, low temperature resistance and high bonding strength.
One of the technical schemes of the invention is as follows:
firstly, dihydric alcohol with a side group is polymerized with alkylene oxide to obtain intermediate refined polyether polyol, and then the intermediate refined polyether polyol is mixed with acid anhydride and polymerized with the alkylene oxide to obtain the polyester polyether polyol.
Preferably, the preparation method of the high-performance polyester ether polyol comprises the following steps:
(1) adding dihydric alcohol with side groups and a catalyst A into a pressure-resistant reaction kettle, mixing, performing nitrogen replacement and vacuum dehydration, adding propylene oxide to perform polymerization reaction, continuing performing internal pressure reaction for 1-1.5 h after the reaction is finished, then vacuumizing to remove unreacted propylene oxide monomers and micromolecular byproducts, and then sequentially performing neutralization, adsorption, drying and filtration to obtain an intermediate refined polyether polyol;
(2) adding the intermediate refined polyether polyol prepared in the step (1), acid anhydride and a catalyst B into a pressure-resistant reaction kettle, mixing, displacing with nitrogen, vacuumizing, heating, adding a first part of propylene oxide to perform an initiation reaction, adding a second part of propylene oxide to perform a polymerization reaction after the reaction activity is opened, continuing performing an internal pressure reaction for 1-1.5 hours after the reaction is finished, and then vacuumizing to remove unreacted propylene oxide monomers and micromolecule byproducts, thereby obtaining the polyester ether polyol.
In the step (1):
the dihydric alcohol with the side group is one or more of 2,2, 4-trimethyl-1, 3-pentanediol, 2, 4-diethyl-1, 5-pentanediol, 2-butyl-2-ethyl-1, 3-propanediol and 3-methyl-1, 5-pentanediol. The use of diols with pendant groups increases the flexibility and hydrolysis resistance of the target polyols.
The mass ratio of the dihydric alcohol with the side group to the propylene oxide is 1: 1-1: 4.
The catalyst A is an alkali metal catalyst, preferably one of KOH, NaOH, potassium alkoxide and sodium alkoxide, and the dosage of the catalyst A is 0.2-0.3% of the molecular weight of the intermediate polyether polyol.
The molecular weight of the prepared intermediate polyether polyol is 400-500, and the hydroxyl value is 220-290 mgKOH/g.
In the synthesis process, nitrogen is replaced until the oxygen content in the kettle is less than 50ppm, vacuum dehydration is carried out until the moisture content of a reaction system is less than 0.03 percent, the vacuum dehydration temperature is 100-115 ℃, the vacuum degree is-0.09 to-0.093 MPa, and the dehydration time is 1-2 hours.
The polymerization reaction temperature of the dihydric alcohol with the side group and the alkylene oxide is 100-115 ℃, and the polymerization reaction time is 2-8 h.
In the step (2):
the acid anhydride is one or more of maleic anhydride, phthalic anhydride, glutaric anhydride, succinic anhydride, citraconic anhydride, itaconic anhydride, 1, 2-cyclopentanedicarboxylic anhydride and cyclopropane-1, 2-dicarboxylic anhydride.
The mass ratio of the intermediate polyether polyol to the anhydride is (2-7) to 1.
The catalyst B is a double metal cyanide complex catalyst, and the dosage of the catalyst B is 0.02-0.06% of the molecular weight of the polyester ether polyol product.
The using amount of the first part of propylene oxide is 8-20% of the mass of the intermediate polyether polyol.
The using amount of the second part of propylene oxide is 2-6% of the mass of the intermediate polyether polyol.
In the synthesis process, nitrogen is replaced until the oxygen content in the kettle is less than 50ppm, the kettle is vacuumized until the vacuum degree is-0.09 to-0.093 MPa, and the temperature is raised to 120 to 160 ℃.
The polymerization reaction temperature of the intermediate refined polyether polyol, the anhydride and the propylene oxide is 120-160 ℃, preferably 135-145 ℃, and the polymerization reaction time is 3-8 h. The ring-opening polymerization of polyether polyol, anhydride and propylene oxide is more facilitated at the reaction temperature.
The second technical scheme of the invention is as follows:
provides a polyether ester polyol prepared by the preparation method, the molecular weight is 1800-2200, the hydroxyl value is 45-70 mgKOH/g, and the viscosity at 25 ℃ is 700-1100 mPas.
The third technical scheme of the invention is as follows:
provides an application of the high-performance polyester ether polyol, which is mainly applied to waterproof coatings.
When the polyester ether polyol is used for the waterproof coating, the polyester ether polyol is matched with polyether triol according to the weight ratio of (2-4) to 1.
As a preferred scheme, 2-5 of the polyester ether polyols with the molecular weights of 1800, 1900, 2000, 2100 and 2200 respectively are mixed according to normal distribution, the relaxation time of a molecular chain can be increased by adopting the method, the mechanical strength of the polyurethane waterproof coating can be regulated and controlled according to actual needs, and the polyurethane waterproof coating with high elongation at break is obtained.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention adopts a unique initiator, designs different molecular structures, and adopts a bimetallic catalytic system to prepare the polyester ether molecular structure containing both 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) compared with the traditional single-component polyurethane waterproof coating, the single-component polyurethane waterproof coating prepared by the invention has the advantages that the elongation at break and the tensile strength can be improved by 20-40%;
(3) the preparation method provided by the invention is scientific, reasonable, simple and feasible, and can realize industrial production by adopting the existing process equipment.
Detailed Description
The present invention will be further described with reference to the following examples, but the present invention is not limited thereto. The materials used in the examples were all commercially available materials except for those specifically mentioned.
Example 1
The preparation method of the polyester ether polyol for the high-performance hydrolysis-resistant waterproof coating comprises the following specific steps:
adding 584g of 2,2, 4-trimethyl-1, 3-pentanediol and 4.15g of KOH into a pressure-resistant reaction kettle, replacing with nitrogen, measuring the oxygen content in the kettle to be less than 50ppm, heating to 100 ℃, keeping the vacuum degree to be-0.093 MPa, vacuumizing and dehydrating for 1h, measuring the moisture content of materials in the kettle to be less than 0.03%, continuously adding 1076g of propylene oxide for polymerization, maintaining the pressure in the kettle to be less than or equal to 0.25MPa in the dropping process, continuing the internal pressure reaction for 1h after the feeding is finished, vacuumizing and dehydrating for 0.5h, cooling to 80 ℃, adding 10.2g of phosphoric acid, 58g of water and 1.66g of magnesium silicate for post-treatment, and performing suction filtration to obtain the intermediate polyether polyol A (the hydroxyl value is 275.9 mgKOH/g).
382.3g of intermediate polyether polyol A, 144.3g of maleic anhydride and 0.9g 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 kettle is vacuumized to-0.09 to-0.093 MPa, the temperature is increased to 135 ℃, 50g of propylene oxide is added for initiating reaction, when the pressure in the reaction kettle is obviously reduced and the temperature is rapidly increased, the catalyst is successfully induced and activated, the temperature in the kettle is controlled to be 140 +/-2 ℃, 1227g of propylene oxide is continuously added for polymerization reaction, after the addition is finished, the internal pressure reaction is continued for 1h, and the monomers are removed by vacuumizing for 0.5h, so that the target polyester polyether polyol 1 (the hydroxyl value is 58.6mgKOH/g, and the viscosity is 798 mPa.
Example 2
The preparation method of the polyester ether polyol for the high-performance hydrolysis-resistant waterproof coating comprises the following specific steps:
adding 472g of 3-methyl-1, 5-pentanediol and 4.1g of KOH into a pressure-resistant reaction kettle, replacing with nitrogen, measuring the oxygen content in the kettle to be less than 50ppm, heating to 100 ℃, keeping the vacuum degree to be-0.093 MPa, vacuumizing and dehydrating for 1h, measuring the moisture content of materials in the kettle to be less than 0.03%, continuously adding 1168g of propylene oxide for polymerization, maintaining the pressure in the kettle to be less than or equal to 0.25MPa in the dropping process, continuing the internal pressure reaction for 1h after the feeding is finished, vacuumizing and removing monomers for 0.5h, cooling to 80 ℃, adding 10.0g of phosphoric acid, 57g of water and 1.64g of magnesium silicate for post-treatment, and performing suction filtration to obtain the intermediate polyether polyol B (hydroxyl value is 279.3 mgKOH/g).
361.6g of intermediate polyether polyol B, 90.9g of maleic anhydride and 0.73g 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 kettle is vacuumized to-0.09 to-0.093 MPa, the temperature is increased to 135 ℃, 40g of propylene oxide is added for initiating reaction, when the pressure in the reaction kettle is obviously reduced and the temperature is rapidly increased, the catalyst is successfully induced and activated, the temperature in the kettle is controlled to be 140 +/-2 ℃, 1326g of propylene oxide is continuously added for polymerization reaction, after the addition is finished, the internal pressure reaction is continued for 1h, and the monomers are removed by vacuumizing for 0.5h, so that the target polyester polyether polyol 2 (the hydroxyl value is 55.7mgKOH/g and the viscosity is 910 mPas) is obtained.
Example 3
The preparation method of the polyester ether polyol for the high-performance hydrolysis-resistant waterproof coating comprises the following specific steps:
adding 640g of 2-butyl-2-ethyl-1, 3-propylene glycol and 4.4g of KOH into a pressure-resistant reaction kettle, replacing with nitrogen, measuring the oxygen content in the kettle to be less than 50ppm, heating to 100 ℃, keeping the vacuum degree to be-0.093 MPa, vacuumizing and dehydrating for 1h, measuring the moisture content of materials in the kettle to be less than 0.03%, continuously adding 1120g of propylene oxide for polymerization, maintaining the pressure in the kettle to be less than or equal to 0.25MPa in the dropping process, continuing the internal pressure reaction for 1h after the feeding is finished, vacuumizing and dehydrating for 0.5h, cooling to 80 ℃, adding 10.8g of phosphoric acid, 62g of water and 1.76g of magnesium silicate for post-treatment, and performing suction filtration to obtain an intermediate polyether polyol C (the hydroxyl value is 260.2 mgKOH/g).
366.5g of intermediate polyether polyol C, 144.2g of citraconic anhydride and 0.73g 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 kettle is vacuumized to-0.09 to-0.093 MPa, the temperature is raised to 135 ℃, 51g of propylene oxide is added for initiating reaction, when the pressure in the reaction kettle is obviously reduced and the temperature is rapidly raised, the catalyst is successfully induced and activated, the temperature in the kettle is controlled to be 140 +/-2 ℃, 1241g of propylene oxide is continuously added for polymerization reaction, after the material is added, the internal pressure reaction is continued for 1h, and the monomers are removed by vacuumizing for 0.5h, so that the target polyester polyether polyol 3 (the hydroxyl value is 53.0mgKOH/g, and the viscosity is 1022 mPas) is obtained.
Comparative example 1
Adding 304g of propylene glycol and 4.15g of KOH into a pressure-resistant reaction kettle, carrying out nitrogen replacement, measuring the oxygen content in the kettle to be less than 50ppm, heating to 100 ℃, keeping the vacuum degree to be-0.093 MPa, carrying out vacuum-pumping dehydration for 1h, measuring the moisture content of the material in the kettle to be less than 0.03%, continuously adding 1356g of propylene oxide for polymerization, keeping the pressure in the kettle to be less than or equal to 0.25MPa in the dropping process, continuing internal pressure reaction for 1h after finishing the charging, carrying out vacuum-pumping de-monomer for 0.5h, cooling to 80 ℃, adding 10.2g of phosphoric acid, 58g of water and 1.66g of magnesium silicate for post-treatment, and carrying out suction filtration to obtain the intermediate polyether polyol D (hydroxyl value of 277.1 mgKOH/g).
382.3g of intermediate polyether polyol D, 144.3g of maleic anhydride and 0.9g 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 kettle is vacuumized to-0.09 to-0.093 MPa, the temperature is increased to 135 ℃, 50g of propylene oxide is added for initiating reaction, when the pressure in the reaction kettle is obviously reduced and the temperature is rapidly increased, the catalyst is successfully induced and activated, the temperature in the kettle is controlled to be 140 +/-2 ℃, 1227g of propylene oxide is continuously added for polymerization reaction, after the addition is finished, the internal pressure reaction is continued for 1h, and the monomers are removed by vacuumizing for 0.5h, so that the target polyester polyether polyol A (the hydroxyl value is 58.8mgKOH/g, and the viscosity is 805 mPas) is obtained.
Comparative example 2
Adding 304g of propylene glycol and 4.1g of KOH into a pressure-resistant reaction kettle, carrying out nitrogen replacement, measuring the oxygen content in the kettle to be less than 50ppm, heating to 100 ℃, keeping the vacuum degree to be-0.093 MPa, carrying out vacuum-pumping dehydration for 1h, measuring the moisture content of the material in the kettle to be less than 0.03%, continuously adding 1336g of propylene oxide for polymerization, keeping the pressure in the kettle to be less than or equal to 0.25MPa in the dropping process, continuing internal pressure reaction for 1h after finishing the charging, carrying out vacuum-pumping de-monomer for 0.5h, cooling to 80 ℃, adding 10.0g of phosphoric acid, 57g of water and 1.64g of magnesium silicate for post-treatment, and carrying out suction filtration to obtain the intermediate polyether polyol E (hydroxyl value is 278.0 mgKOH/g).
361.6g of intermediate polyether polyol E, 90.9g of maleic anhydride and 0.73g 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 kettle is vacuumized to-0.09 to-0.093 MPa, the temperature is increased to 135 ℃, 40g of propylene oxide is added for initiating reaction, when the pressure in the reaction kettle is obviously reduced and the temperature is rapidly increased, the catalyst is successfully induced and activated, the temperature in the kettle is controlled to be 140 +/-2 ℃, 1326g of propylene oxide is continuously added for polymerization reaction, after the addition is finished, the internal pressure reaction is continued for 1h, and the monomers are removed by vacuumizing for 0.5h, so that the target polyester polyether polyol B (the hydroxyl value is 55.4mgKOH/g and the viscosity is 924 mPas) is obtained.
Comparative example 3
Adding 424g of diethylene glycol and 4.4g of KOH into a pressure-resistant reaction kettle, performing nitrogen replacement, measuring the oxygen content in the kettle to be less than 50ppm, heating to 100 ℃, keeping the vacuum degree to be minus 0.093MPa, performing vacuum-pumping dehydration for 1h, measuring the moisture content of materials in the kettle to be less than 0.03%, continuously adding 1336g of propylene oxide for polymerization, keeping the pressure in the kettle to be less than or equal to 0.25MPa in the dropping process, continuing internal pressure reaction for 1h after the charging is finished, performing vacuum-pumping de-monomer for 0.5h, cooling to 80 ℃, adding 10.8g of phosphoric acid, 62g of water and 1.76g of magnesium silicate for post-treatment, and performing suction filtration to obtain an intermediate polyether polyol F (hydroxyl value of 261.4 mgKOH/g).
366.5g of intermediate polyether polyol F, 144.2g of citraconic anhydride and 0.73g 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 kettle is vacuumized to-0.09 to-0.093 MPa, the temperature is raised to 135 ℃, 51g of propylene oxide is added for initiating reaction, when the pressure in the reaction kettle is obviously reduced and the temperature is rapidly raised, the catalyst is successfully induced and activated, the temperature in the kettle is controlled to be 140 +/-2 ℃, 1241g of propylene oxide is continuously added for polymerization reaction, after the material is added, the internal pressure reaction is continued for 1h, and the monomers are removed by vacuumizing for 0.5h, so that the target polyester polyether polyol C (the hydroxyl value is 52.5mgKOH/g, and the viscosity is 1039 mPas) is obtained.
Examples 4 to 6 and comparative examples 4 to 8
The polyester ether polyols prepared in examples 1 to 3 and comparative examples 1 to 3 were used in a waterproof coating material, and the raw material composition thereof is shown in table 1 in parts by weight. Wherein the waterproof coating formulations of examples 4-6 correspond to the polyester ether polyols prepared in examples 1-3, respectively, the waterproof coating formulations of comparative examples 4-6 correspond to the polyester ether polyols prepared in comparative examples 1-3, respectively, and the formulations of comparative examples 7-8 do not contain polyester ether polyols.
The polyether triol is obtained from INOVOL F330N, a commercially available product of Shandong-Nowei New Material Co.
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.
The plasticizer used was cyclohexane-1, 2-dicarboxylic acid diisononyl ester, a commercial product of basf, germany.
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:
polyether triol, polyester diol/polyester ether polyol, a plasticizer and a filler are put into a reaction kettle, dispersed uniformly at a high speed, vacuumized to-0.093 MPa, heated to 110 ℃ and dehydrated 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 4-6 and comparative examples 1-2 were respectively mixed uniformly, and the mixture was coated on a mold coated with a release agent uniformly by a squeegee for 2-3 times to give a final coating film thickness of 1.5mm, and the final coating film was cured for 7 days under standard test conditions of (23 + -2) DEG C and relative humidity (50 + -5)% and tested for coating film performance according to the method of 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 4-6 and comparative examples 4-8
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, elongation at break and hydrolysis resistance than the product obtained in the comparative example under the same conditions.
Claims (10)
1. A preparation method of high-performance polyester ether polyol is characterized by comprising the following steps: polymerizing dihydric alcohol with a side group with alkylene oxide to obtain intermediate refined polyether polyol, mixing the intermediate refined polyether polyol with acid anhydride, and polymerizing the mixture with the alkylene oxide to obtain polyester polyether polyol;
the dihydric alcohol with the side group is one or more of 2,2, 4-trimethyl-1, 3-pentanediol, 2, 4-diethyl-1, 5-pentanediol, 2-butyl-2-ethyl-1, 3-propanediol and 3-methyl-1, 5-pentanediol.
2. The process for preparing a high performance polyester ether polyol according to claim 1, characterized in that: the method comprises the following steps:
(1) adding dihydric alcohol with side groups and a catalyst A into a pressure-resistant reaction kettle, mixing, performing nitrogen replacement and vacuum dehydration, adding propylene oxide to perform polymerization reaction, continuing performing internal pressure reaction for 1-1.5 h after the reaction is finished, then vacuumizing to remove unreacted propylene oxide monomers and micromolecular byproducts, and then sequentially performing neutralization, adsorption, drying and filtration to obtain an intermediate refined polyether polyol;
(2) adding the intermediate refined polyether polyol prepared in the step (1), acid anhydride and a catalyst B into a pressure-resistant reaction kettle, mixing, displacing with nitrogen, vacuumizing, heating, adding a first part of propylene oxide to perform an initiation reaction, adding a second part of propylene oxide to perform a polymerization reaction after the reaction activity is opened, continuing performing an internal pressure reaction for 1-1.5 hours after the reaction is finished, and then vacuumizing to remove unreacted propylene oxide monomers and micromolecule byproducts, thereby obtaining the polyester ether polyol.
3. The process for preparing a high performance polyester ether polyol according to claim 2, characterized in that: the mass ratio of the dihydric alcohol with the side group to the propylene oxide is 1: 1-1: 4.
4. The process for preparing a high performance polyester ether polyol according to claim 2, characterized in that: the catalyst A is alkali metal catalyst, and the dosage of the catalyst A is 0.2-0.3% of the molecular weight of the intermediate polyether polyol.
5. The process for preparing a high performance polyester ether polyol according to claim 2, characterized in that: the molecular weight of the prepared intermediate polyether polyol is 400-500, and the hydroxyl value is 220-290 mgKOH/g.
6. The process for preparing a high performance polyester ether polyol according to claim 2, 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-cyclopentanedicarboxylic anhydride and cyclopropane-1, 2-dicarboxylic anhydride; the mass ratio of the intermediate polyether polyol to the anhydride is (2-7) to 1.
7. The process for preparing a high performance polyester ether polyol according to claim 2, characterized in that: the catalyst B is a double metal cyanide complex catalyst, and the dosage of the catalyst B is 0.02-0.06% of the molecular weight of the polyester ether polyol product.
8. The process for preparing a high performance polyester ether polyol according to claim 2, characterized in that: the using amount of the first part of propylene oxide is 8-20% of the mass of the intermediate polyether polyol; the using amount of the second part of propylene oxide is 2-6% of the mass of the intermediate polyether polyol.
9. A high performance polyester ether polyol characterized by: the molecular weight is 1800-2200, the hydroxyl value is 45-70 mgKOH/g, and the viscosity at 25 ℃ is 700-1100 mPa.s.
10. Use of a high performance polyester ether polyol according to claim 9 wherein: the polyether triol is matched with polyether triol according to the weight ratio of (2-4) to 1 for use, and the polyether triol is applied to waterproof paint.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111441635.1A CN114369236B (en) | 2021-11-30 | 2021-11-30 | High-performance polyester ether polyol, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111441635.1A CN114369236B (en) | 2021-11-30 | 2021-11-30 | High-performance polyester ether polyol, and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114369236A true CN114369236A (en) | 2022-04-19 |
| CN114369236B CN114369236B (en) | 2024-04-12 |
Family
ID=81140921
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111441635.1A Active CN114369236B (en) | 2021-11-30 | 2021-11-30 | High-performance polyester ether polyol, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114369236B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115010901A (en) * | 2022-06-17 | 2022-09-06 | 佳化化学科技发展（上海）有限公司 | Low-viscosity hydrolysis-resistant photocuring polyurethane resin and preparation method and application thereof |
| CN115304761A (en) * | 2022-08-11 | 2022-11-08 | 山东一诺威新材料有限公司 | Polyester ether polyol for high-performance polyurethane waterproof coating and preparation method thereof |
Citations (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3455886A (en) * | 1965-02-18 | 1969-07-15 | Columbian Carbon | Thermoplastic polyols containing polyester-ether blocks |
| US5070172A (en) * | 1987-01-22 | 1991-12-03 | Kuraray Co., Ltd. | Process for producing polyurethane |
| CN1214060A (en) * | 1996-03-20 | 1999-04-14 | 阿科化学技术公司 | Polyetherester resins from diol diesters |
| JP2001055555A (en) * | 1999-08-19 | 2001-02-27 | Dainippon Ink & Chem Inc | Adhesive composition for lamination |
| JP2002020446A (en) * | 2000-07-04 | 2002-01-23 | Nippon Polyurethane Ind Co Ltd | Urethane elastomer-forming composition for industrial apparatus part and production method for urethane elastomer for industrial apparatus part by using the same |
| CN1431240A (en) * | 2001-11-19 | 2003-07-23 | 中国科学院山西煤炭化学研究所 | Method for preparing polyether ester polyalcohol |
| US20070142489A1 (en) * | 2005-12-21 | 2007-06-21 | Kao Corporation | Method for producing polyurethane foam |
| CN1986594A (en) * | 2005-12-21 | 2007-06-27 | 花王株式会社 | Method for producing polyurethane foam |
| CN101024684A (en) * | 2007-01-29 | 2007-08-29 | 青岛科技大学 | Polyester ether polylol and its preparing method |
| CN101142251A (en) * | 2005-03-17 | 2008-03-12 | 巴斯福股份公司 | Polyurethane shoe soles |
| JP2008133459A (en) * | 2006-10-27 | 2008-06-12 | Asahi Glass Co Ltd | One-pack moisture-curable composition |
| CN102070766A (en) * | 2010-12-27 | 2011-05-25 | 沈阳化工大学 | Method for preparing novel polyether-polyester polyurethane material |
| CN102471478A (en) * | 2009-07-03 | 2012-05-23 | 拜尔材料科学股份公司 | Process for preparing polyether polyols containing terminal primary hydroxyl groups |
| EP2636694A1 (en) * | 2012-03-09 | 2013-09-11 | Novance | Polyester polyether polyol |
| CN104072745A (en) * | 2014-07-04 | 2014-10-01 | 山东一诺威新材料有限公司 | Method for preparing polyether polyol for aromatic coating |
| CN104650330A (en) * | 2013-11-18 | 2015-05-27 | 上海凯众材料科技股份有限公司 | Preparation method of polyester dihydric alcohol and microcellular polyurethane elastomer |
| CN105153410A (en) * | 2015-07-07 | 2015-12-16 | 北京市建筑工程研究院有限责任公司 | Preparation method of flame retardant polyester ether polyol |
| CN105504259A (en) * | 2015-12-29 | 2016-04-20 | 浙江华峰新材料股份有限公司 | Polyurethane resin, preparation method thereof and application thereof to micro cellular elastomer |
| JP2017036388A (en) * | 2015-08-10 | 2017-02-16 | 川崎化成工業株式会社 | Polyurethane foam and manufacturing method therefor |
| CN109863189A (en) * | 2016-10-13 | 2019-06-07 | 巴斯夫欧洲公司 | Radiation-hardenable composition containing polyester acrylate |
| CN110776627A (en) * | 2019-10-25 | 2020-02-11 | 湖北回天新材料(宜城)有限公司 | Polyester polyol for solvent-free adhesive and preparation method and application thereof |
| CN111560110A (en) * | 2020-06-05 | 2020-08-21 | 旭川化学（苏州）有限公司 | Moisture-absorption-resistant aqueous polyurethane dispersion and preparation method and application thereof |
| CN113528076A (en) * | 2020-12-31 | 2021-10-22 | 上海回天新材料有限公司 | Solvent-free single-component moisture-curing polyurethane adhesive for wearable equipment and preparation method thereof |
-
2021
- 2021-11-30 CN CN202111441635.1A patent/CN114369236B/en active Active
Patent Citations (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3455886A (en) * | 1965-02-18 | 1969-07-15 | Columbian Carbon | Thermoplastic polyols containing polyester-ether blocks |
| US5070172A (en) * | 1987-01-22 | 1991-12-03 | Kuraray Co., Ltd. | Process for producing polyurethane |
| CN1214060A (en) * | 1996-03-20 | 1999-04-14 | 阿科化学技术公司 | Polyetherester resins from diol diesters |
| JP2001055555A (en) * | 1999-08-19 | 2001-02-27 | Dainippon Ink & Chem Inc | Adhesive composition for lamination |
| JP2002020446A (en) * | 2000-07-04 | 2002-01-23 | Nippon Polyurethane Ind Co Ltd | Urethane elastomer-forming composition for industrial apparatus part and production method for urethane elastomer for industrial apparatus part by using the same |
| CN1431240A (en) * | 2001-11-19 | 2003-07-23 | 中国科学院山西煤炭化学研究所 | Method for preparing polyether ester polyalcohol |
| CN101142251A (en) * | 2005-03-17 | 2008-03-12 | 巴斯福股份公司 | Polyurethane shoe soles |
| US20070142489A1 (en) * | 2005-12-21 | 2007-06-21 | Kao Corporation | Method for producing polyurethane foam |
| CN1986594A (en) * | 2005-12-21 | 2007-06-27 | 花王株式会社 | Method for producing polyurethane foam |
| JP2008133459A (en) * | 2006-10-27 | 2008-06-12 | Asahi Glass Co Ltd | One-pack moisture-curable composition |
| CN101024684A (en) * | 2007-01-29 | 2007-08-29 | 青岛科技大学 | Polyester ether polylol and its preparing method |
| CN102471478A (en) * | 2009-07-03 | 2012-05-23 | 拜尔材料科学股份公司 | Process for preparing polyether polyols containing terminal primary hydroxyl groups |
| CN102070766A (en) * | 2010-12-27 | 2011-05-25 | 沈阳化工大学 | Method for preparing novel polyether-polyester polyurethane material |
| EP2636694A1 (en) * | 2012-03-09 | 2013-09-11 | Novance | Polyester polyether polyol |
| CN104650330A (en) * | 2013-11-18 | 2015-05-27 | 上海凯众材料科技股份有限公司 | Preparation method of polyester dihydric alcohol and microcellular polyurethane elastomer |
| CN104072745A (en) * | 2014-07-04 | 2014-10-01 | 山东一诺威新材料有限公司 | Method for preparing polyether polyol for aromatic coating |
| CN105153410A (en) * | 2015-07-07 | 2015-12-16 | 北京市建筑工程研究院有限责任公司 | Preparation method of flame retardant polyester ether polyol |
| JP2017036388A (en) * | 2015-08-10 | 2017-02-16 | 川崎化成工業株式会社 | Polyurethane foam and manufacturing method therefor |
| CN105504259A (en) * | 2015-12-29 | 2016-04-20 | 浙江华峰新材料股份有限公司 | Polyurethane resin, preparation method thereof and application thereof to micro cellular elastomer |
| CN109863189A (en) * | 2016-10-13 | 2019-06-07 | 巴斯夫欧洲公司 | Radiation-hardenable composition containing polyester acrylate |
| CN110776627A (en) * | 2019-10-25 | 2020-02-11 | 湖北回天新材料(宜城)有限公司 | Polyester polyol for solvent-free adhesive and preparation method and application thereof |
| CN111560110A (en) * | 2020-06-05 | 2020-08-21 | 旭川化学（苏州）有限公司 | Moisture-absorption-resistant aqueous polyurethane dispersion and preparation method and application thereof |
| CN113528076A (en) * | 2020-12-31 | 2021-10-22 | 上海回天新材料有限公司 | Solvent-free single-component moisture-curing polyurethane adhesive for wearable equipment and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 谢静: "侧基对聚氨酯耐水解性影响研究", 《中国优秀硕士学位论文全文数据库 (工程科技Ⅰ辑)》, no. 5 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115010901A (en) * | 2022-06-17 | 2022-09-06 | 佳化化学科技发展（上海）有限公司 | Low-viscosity hydrolysis-resistant photocuring polyurethane resin and preparation method and application thereof |
| CN115304761A (en) * | 2022-08-11 | 2022-11-08 | 山东一诺威新材料有限公司 | Polyester ether polyol for high-performance polyurethane waterproof coating and preparation method thereof |
| CN115304761B (en) * | 2022-08-11 | 2023-12-12 | 山东一诺威新材料有限公司 | Polyester ether polyol for high-performance polyurethane waterproof coating and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114369236B (en) | 2024-04-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114369236B (en) | High-performance polyester ether polyol, and preparation method and application thereof | |
| Shendi et al. | Synthesis and characterization of a novel internal emulsifier derived from sunflower oil for the preparation of waterborne polyurethane and their application in coatings | |
| EP3183282B1 (en) | Polyester modified polybutadienols for the production of polyurethane elastomers and thermoplastic polyurethanes | |
| CN101182405B (en) | Preparation method of dual-component aqueous polyurethane adhesive agent | |
| CN102140243B (en) | Plastic sizing agent for silane-modified single component wet cured polyurethane playing court and preparation method thereof | |
| CN103703038B (en) | Aqueous polyurethane resin dispersion and application thereof | |
| CN107446457A (en) | Solventless method prepares aqueous acrylic modified polyurethane hybrid resin | |
| EP3328915B1 (en) | New high molecular weight polymers from waste raw materials | |
| CN113817434B (en) | Halogen-containing flame-retardant polyurethane hot melt adhesive and preparation method thereof | |
| WO2016120406A1 (en) | A polyurethane adhesive formulation based on polyether carbonate polyol | |
| JP2009132832A (en) | One-component type polyurethane-based curable composition and adhesive using this | |
| CN115304761B (en) | Polyester ether polyol for high-performance polyurethane waterproof coating and preparation method thereof | |
| CN115956095A (en) | Hydrophilic acrylic modified polyurethane, preparation method thereof, water-based coating composition prepared from hydrophilic acrylic modified polyurethane and preparation method of water-based coating composition | |
| EP3981814B1 (en) | Polyol composition comprising anhydrosugar alcohols and anhydrosugar alcohol polymer | |
| KR102271145B1 (en) | Isocyanate prepolymer, moisture-curing polyurethane and eco-friendly adhesive composition comprising the same | |
| CN110128613B (en) | Waterborne polyurethane for leather with high water vapor permeability | |
| KR20140125736A (en) | Unsaturated polycarbonate diol, procedure to obtain such polycarbonate diol and its use | |
| KR102434783B1 (en) | Acryl-modified polyurethane composition and method for preparing the same, and waterborne coating composition prepared therefrom and method for preparing the same | |
| CN114276747A (en) | Ultralow-temperature-resistant easy-construction single-component polyurethane waterproof coating and preparation method thereof | |
| CN110128996B (en) | Sealant, preparation method and application thereof and vehicle | |
| CN111205426B (en) | Preparation method of low-temperature-resistant polyurethane elastomer | |
| KR102161123B1 (en) | Anhydrodugar alcohol-based composition crosslinked with aromatic ether-based epoxy compound and polyol composition prepared by adding alkylene oxide thereto | |
| CN113105617A (en) | Preparation method of polyether polyol for high-performance waterproof coating | |
| CN114989414B (en) | Photo-thermal composite curing polytetrahydrofuran oligomer | |
| CN116904102B (en) | Single-component polyurethane waterproof paint and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |