CN116904102A - Single-component polyurethane waterproof paint and preparation method thereof - Google Patents
Single-component polyurethane waterproof paint and preparation method thereof Download PDFInfo
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- CN116904102A CN116904102A CN202311167858.2A CN202311167858A CN116904102A CN 116904102 A CN116904102 A CN 116904102A CN 202311167858 A CN202311167858 A CN 202311167858A CN 116904102 A CN116904102 A CN 116904102A
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- CN
- China
- Prior art keywords
- polyether polyol
- polyurethane waterproof
- furan
- component polyurethane
- curing agent
- 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.)
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Links
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 57
- 239000004814 polyurethane Substances 0.000 title claims abstract description 56
- 239000003973 paint Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 150000003077 polyols Chemical class 0.000 claims abstract description 67
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 51
- 229920000570 polyether Polymers 0.000 claims abstract description 51
- 229920005862 polyol Polymers 0.000 claims abstract description 48
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 29
- 238000000576 coating method Methods 0.000 claims abstract description 27
- 239000011248 coating agent Substances 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- 239000002131 composite material Substances 0.000 claims abstract description 17
- 239000004970 Chain extender Substances 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 12
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000007822 coupling agent Substances 0.000 claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- PARWUHTVGZSQPD-UHFFFAOYSA-N phenylsilane Chemical compound [SiH3]C1=CC=CC=C1 PARWUHTVGZSQPD-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000945 filler Substances 0.000 claims abstract description 8
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 6
- 239000004014 plasticizer Substances 0.000 claims abstract description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 18
- -1 phenol diol Chemical class 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000003999 initiator Substances 0.000 claims description 10
- 230000018044 dehydration Effects 0.000 claims description 9
- 238000006297 dehydration reaction Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- KLDXJTOLSGUMSJ-JGWLITMVSA-N Isosorbide Chemical compound O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 KLDXJTOLSGUMSJ-JGWLITMVSA-N 0.000 claims description 8
- 125000002947 alkylene group Chemical group 0.000 claims description 8
- 229960002479 isosorbide Drugs 0.000 claims description 8
- QWBBPBRQALCEIZ-UHFFFAOYSA-N 2,3-dimethylphenol Chemical compound CC1=CC=CC(O)=C1C QWBBPBRQALCEIZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims description 6
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 claims description 6
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 claims description 4
- CVQVSVBUMVSJES-UHFFFAOYSA-N dimethoxy-methyl-phenylsilane Chemical compound CO[Si](C)(OC)C1=CC=CC=C1 CVQVSVBUMVSJES-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims 1
- 125000003118 aryl group Chemical group 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 16
- 230000000694 effects Effects 0.000 abstract 1
- 150000005846 sugar alcohols Polymers 0.000 abstract 1
- 230000002195 synergetic effect Effects 0.000 abstract 1
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 12
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 12
- 239000003921 oil Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 239000005995 Aluminium silicate Substances 0.000 description 6
- 235000012211 aluminium silicate Nutrition 0.000 description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 description 6
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical group COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 6
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 6
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical group O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 6
- 239000012188 paraffin wax Substances 0.000 description 6
- 238000005227 gel permeation chromatography Methods 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- 229920002121 Hydroxyl-terminated polybutadiene Polymers 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 230000000977 initiatory effect Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003672 ureas Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RVGRUAULSDPKGF-UHFFFAOYSA-N Poloxamer Chemical compound C1CO1.CC1CO1 RVGRUAULSDPKGF-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 235000003704 aspartic acid Nutrition 0.000 description 1
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- NSPSPMKCKIPQBH-UHFFFAOYSA-K bismuth;7,7-dimethyloctanoate Chemical compound [Bi+3].CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O NSPSPMKCKIPQBH-UHFFFAOYSA-K 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/487—Polyethers containing cyclic groups
- C08G18/4879—Polyethers containing cyclic groups containing aromatic 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
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/487—Polyethers containing cyclic groups
- C08G18/4883—Polyethers containing cyclic groups containing cyclic groups having at least one oxygen atom in the ring
-
- 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
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Paints Or Removers (AREA)
Abstract
The invention belongs to the technical field of waterproof coatings, and particularly relates to a single-component polyurethane waterproof coating and a preparation method thereof. The single-component polyurethane waterproof paint provided by the invention comprises the following raw materials: polyether polyol with furan-like structure, polydimethyl phenol dihydric alcohol, phenylsilane coupling agent, composite latent curing agent, plasticizer, filler, toluene diisocyanate, catalyst, chain extender and viscosity reducer; according to the invention, furan-like structural rigid groups are introduced into a polyether main chain, and the polydimethyl phenol dihydric alcohol is introduced into a formula system, so that the hard segment content in a polyurethane chain segment is improved, the polyurethane chain segment has better compatibility with furan-like structural polyether polyhydric alcohol, the mechanical strength of the material is synergistically improved, the elongation of the polyurethane material is not influenced, the synergistic enhancement effect is exerted with a phenylsilane coupling agent and a composite latent curing agent, and the mechanical property of the polyurethane waterproof coating is greatly improved.
Description
Technical Field
The invention belongs to the technical field of waterproof coatings, and particularly relates to a single-component polyurethane waterproof coating and a preparation method thereof.
Background
The polyurethane waterproof coating has good mechanical property, adhesiveness, wear resistance and chemical corrosion resistance, is convenient to maintain and construct, and has wide application in the fields of construction, rail transit, home decoration and the like. The waterproof coating can be divided into a single-component polyurethane waterproof coating and a double-component polyurethane waterproof coating according to the composition, and compared with the double-component polyurethane waterproof coating, the single-component waterproof coating can be used on site, is convenient to construct, does not need to use large-scale mixing equipment for operation, has low requirement on the water content of a base surface, and can be constructed under the condition of high humidity.
In order to reduce the cost of the waterproof coating, manufacturers of single-component polyurethane waterproof coatings continuously increase the powder content (about 50%), so that the mechanical properties are generally poor, for example, the national standard I-type single-component polyurethane waterproof coating specified in GB19250-2013 requires that the tensile strength be more than or equal to 2MPa, the elongation be more than or equal to 500% and the tearing strength be more than or equal to 15N/mm; when the effective components of polyurethane are improved, the cost is obviously increased, and the low cost and the high performance become contradiction gradually, so that the further application of the polyurethane waterproof coating is hindered. The bisphenol A polyether and the castor oil modified polyol are added into the formula of the patent CN110684457B to improve the mechanical property, the tensile strength of the single-component polyurethane waterproof paint is higher than 20MPa, and the elongation at break is higher than 450%; the mechanical property of the polyurethane waterproof paint is improved by adopting epoxy resin in the patent CN 105315878B; the patent CN110951391B uses hydroxyl-terminated polybutadiene to realize mild curing, and the molecular structure of the hydroxyl-terminated polybutadiene does not contain ether bonds, so that the hydroxyl-terminated polybutadiene is stable to water, and the influence of the hydroxyl-terminated polybutadiene on mechanical properties is reduced; the patent CN113444441A utilizes the aspartic acid ester and isocyanate to carry out polymerization reaction according to a quantitative proportion to generate urea compounds, and then the urea compounds are matched with components such as a latent curing agent, a catalyst and the like, so that the obtained modified single-component polyurethane waterproof coating has higher tensile strength, tear strength, bonding strength with a cement base surface and other mechanical properties. The modification method has relatively high manufacturing cost and relatively complex raw material system, and is not beneficial to industrialized popularization. The polyurethane waterproof industry is urgent to find a method for improving the mechanical properties of the waterproof coating, and the application range of the polyurethane waterproof coating is further improved.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide the single-component polyurethane waterproof coating, wherein a rigid group is introduced into a polyurethane structure, so that the mechanical property of the polyurethane waterproof coating is improved, and the problem that the mechanical property of the traditional single-component polyurethane waterproof coating is insufficient under the condition of high filler content is solved.
The invention also provides a preparation method thereof, which is suitable for mass production.
The single-component polyurethane waterproof paint provided by the invention comprises the following raw materials:
polyether polyol with furan-like structure, polydimethyl phenol dihydric alcohol, phenylsilane coupling agent, composite latent curing agent, plasticizer, filler, toluene diisocyanate, catalyst, chain extender and viscosity reducer;
wherein:
the number average molecular weight of the polyether polyol with the furan-like structure is 2000-3000g/mol, and the hydroxyl value is 44-55mgKOH/g;
the polyether polyol with the furan-like structure is obtained by adopting a composite initiator and ring-opening polymerization of alkylene oxide;
the composite initiator is a mixture of polyether polyol with functionality of 2 and number average molecular weight of 400g/mol (preferably INOVOL C204 manufactured by Shandong Yinuowei New material Co., ltd.), isosorbide and polyether polyol with functionality of 3 and number average molecular weight of 500g/mol (preferably INOVOL C305 manufactured by Shandong Yinuowei New material Co., ltd.).
The polyether polyol with the furan-like structure is obtained by adopting a composite initiator and a bimetallic catalyst to catalyze ring-opening polymerization of alkylene oxide, and the structural formula of the polyether polyol with the furan-like structure is shown as follows;
wherein: m is more than or equal to 30 and less than or equal to 45, n is more than or equal to 1 and less than or equal to 5.
The mass ratio of the alkylene oxide to the composite initiator is (6-10): 1.
The dosage of the bimetallic catalyst is 100-200 ppm.
The ring-opening polymerization reaction temperature is 130-145 ℃.
The preparation method of the polyether polyol with the furan-like structure comprises the following steps: adding INOVOL C204, isosorbide, INOVOL C305 and a bimetallic catalyst into a pressure-resistant reaction kettle, after nitrogen replacement, heating to 100 ℃ for dehydration for 2h, heating to 130 ℃ for dropwise adding propylene oxide for initiation, after the pressure is reduced to-0.08 MPa, feeding a first section of propylene oxide (25-45 wt.% of alkylene oxide), continuously feeding propylene oxide-ethylene oxide mixed liquid (the mass ratio of propylene oxide to ethylene oxide is 10:1), controlling the pressure to be not more than 0.40MPa, reacting at 130-145 ℃ for internal pressure for 2h, and removing monomers for 0.5h to obtain the polyether polyol with a furan-like structure.
The number average molecular weight of the polydimethyl phenol diol is 1000-3000g/mol, and the mass ratio of the polydimethyl phenol diol to the polyether polyol with furan-like structure is (1-3): 100. Preferably, the polydichlorophenol diol is produced by Saint Foundation industries, inc. (China) and Dalianzhong chemical Co., ltd.
The phenylsilane coupling agent is one or more of phenyltriethoxysilane, phenylmethyldimethoxysilane, diphenyldimethoxysilane and phenyltrimethoxysilane, and the proportion of the phenyltrimethoxysilane coupling agent in the total amount of the raw materials is 1-3 wt%.
The composite latent curing agent is a mixture of an aliphatic imine type latent curing agent and an aromatic imine type latent curing agent.
The mass ratio of the aliphatic imine type latent curing agent to the aromatic imine type latent curing agent is (2-3) 1, and the ratio of the aliphatic imine type latent curing agent to the aromatic imine type latent curing agent in the total amount of raw materials is 0.8-1.5wt.%. The aliphatic imine type latent curing agent is preferably XY-3767, and the aromatic imine type latent curing agent is preferably XY-401.
The plasticizer is preferably chlorinated paraffin;
the viscosity reducer is preferably dimethyl carbonate and solvent oil;
the ratio of the catalyst in the total amount of the raw materials is 1-3 wt%;
the ratio of the chain extender in the total amount of the raw materials is 3-5 wt%;
the filler is kaolin, calcium carbonate and talcum powder, and the proportion of the filler in the total amount of the raw materials is 40-60wt.%.
The preparation method of the single-component polyurethane waterproof paint comprises the following steps:
and uniformly mixing polyether polyol with a furan-like structure, poly (dimethylphenol) dihydric alcohol, a plasticizer, a filler and a phenylsilane coupling agent, heating to 100 ℃ for dehydration for 2 hours, cooling to 80 ℃, adding toluene diisocyanate, a catalyst and a chain extender, heating to 90 ℃ for reaction for 2 hours, adding a latent curing agent and a viscosity reducer, stirring, defoaming and discharging to obtain the single-component polyurethane waterproof coating.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the invention, a fused furan ring is introduced into a raw material chemical structure through polyether synthesis, so that the rigid structure ratio of a polyurethane main chain is improved.
(2) According to the invention, the polydimethyl phenol dihydric alcohol is introduced into a formula system, so that the hard segment content in the polyurethane chain segment is improved, the polyurethane chain segment has better compatibility with polyether polyol with a furan-like structure, and the mechanical strength of the material is cooperatively improved without influencing the elongation of the polyurethane material.
(3) The invention adopts the phenyl silane coupling agent with large steric hindrance structure and the composite latent curing agent, so that the waterproof material has higher bonding strength with the base material, and the mechanical property of the waterproof material is further improved.
Drawings
FIG. 1 is a GPC chart of a furan-like structure polyether polyol (1);
FIG. 2 is a GPC chart of a furan-like structure polyether polyol (2);
FIG. 3 is a GPC chart of a furan-like structure polyether polyol (3);
FIG. 4 is an infrared spectrum of a furan-like structure of polyether polyol (1);
FIG. 5 is an infrared spectrum of a furan-like structure of polyether polyol (2);
FIG. 6 is an infrared spectrum of a polyether polyol (3) of furan-like structure.
Detailed Description
The invention is further illustrated by the following examples.
All materials used in the examples are commercially available, except as specified.
Polyether polyol:
inonol C204, new material inc. Eastern norwegian (2 functionality, 400 number average molecular weight);
inonol C305, new material inc. Northwest, shandong (3 functionality, 500 number average molecular weight);
inonol C220, new material inc. Northwest, shandong (2 functionality, 2000 number average molecular weight);
inonol F330N, new material inc. Shandong monowive (3 functionality, 5000 number average molecular weight);
phenyltriethoxysilane: SCA-P61E, nanjing Neodder New Material technologies Co., ltd;
phenylmethyldimethoxysilane: SCA-P61T, nanjing Neodder New Material technologies Co., ltd;
diphenyl dimethoxy silane: SCA-P62M, nanjing Neodder New Material technologies Co., ltd;
phenyl trimethoxysilane: SCA-P61M, nanjing Neodder New Material technologies Co., ltd;
isosorbide, pharmaceutical grade, shandong Tianli pharmaceutical Co., ltd;
isocyanate: toluene diisocyanate, T-80, shanghai Basex polyurethane Co., ltd;
bimetallic catalyst: huaian polyurethane science and technology Co., ltd;
solvent oil: 150# solvent oil, shandong Xuexiang chemical Co., ltd;
catalyst: bismuth neodecanoate, hangzhou Jiuxi chemical Co., ltd;
chain extender: a-95, win the creation of specialty Chemie Co., ltd.
Preparation of polyether polyol (1) of furan-like structure:
260g of INOVOL C204, 29.2g of isosorbide, 75g of INOVOL C305 and 0.258g of bimetallic catalyst are added into a pressure-resistant reaction kettle, after nitrogen is replaced for 3 times, the temperature is raised to 100 ℃ for dehydration for 2 hours, the temperature is raised to 130 ℃, 38g of propylene oxide is added dropwise for initiation, after the pressure is reduced to minus 0.08MPa, 901.8g of propylene oxide is added, 1160g of mixed liquid of propylene oxide and 110g of ethylene oxide is continuously fed, the pressure in the reaction process is controlled to be not more than 0.40MPa, the reaction temperature is 137.5+/-7.5 ℃, the internal pressure is controlled to react for 2 hours, and the demonomerization is carried out for 0.5 hours, thus obtaining the polyether polyol (1). The test hydroxyl value was 49.0mgKOH/g, viscosity was 537 mPas, pH5.8 and acid value was 0.049mgKOH/g.
Preparation of furan-like polyether polyol (2):
160g of INOVOL C204, 58.4g of isosorbide, 75g of INOVOL C305 and 0.52g of bimetallic catalyst are added into a pressure-resistant reaction kettle, after nitrogen is replaced for 3 times, the temperature is raised to 100 ℃ for dehydration for 2 hours, the temperature is raised to 130 ℃, 35g of propylene oxide is added dropwise for initiation, after the pressure is reduced to minus 0.08MPa, 886.6g of propylene oxide is added, 1350g of mixed liquid of propylene oxide and 135g of ethylene oxide is continuously fed, the pressure in the reaction process is controlled to be not more than 0.40MPa, the reaction temperature is 137.5+/-7.5 ℃, the internal pressure is reacted for 2 hours, and the monomer is removed for 0.5 hours, so that the polyether polyol (2) with a furan-like structure is obtained. The test hydroxyl value was 44.6mgKOH/g, the viscosity was 624 mPas, the pH was 6.5 and the acid value was 0.039mgKOH/g.
Preparation of polyether polyol (3) of furan-like structure:
adding 40g of INOVOL C204, 114g of isosorbide, 50g of INOVOL C305 and 0.44g of a bimetallic catalyst into a pressure-resistant reaction kettle, carrying out nitrogen substitution for 3 times, heating to 100 ℃ for dehydration for 2 hours, heating to 130 ℃, dropwise adding 42g of propylene oxide for initiation, reducing the pressure to-0.08 MPa, feeding 565g of propylene oxide, continuously feeding 130g of ethylene oxide mixed liquid of 1300g of propylene oxide, controlling the pressure in the reaction process to be not more than 0.40MPa, carrying out internal pressure reaction for 2 hours at 137.5+/-7.5 ℃, and carrying out demonomerization for 0.5 hour, thereby obtaining the polyether polyol (3) with the furan-like structure. The test hydroxyl value was 55.0mgKOH/g, viscosity 514 mPas, pH7.0 and acid value 0.041mgKOH/g.
The preparation of the single-component polyurethane waterproof paint comprises the following steps:
example 1
Mixing 180g of polyether polyol (1) with a furan-like structure, 2g of poly (dimethylphenol) glycol (with a number average molecular weight of 2000 g/mol), 100g of chlorinated paraffin, 100g of kaolin, 200g of calcium carbonate, 200g of talcum powder and 1g of phenyl triethoxysilane, dispersing, heating to 100 ℃ for dehydration and timing for 2 hours, cooling to 80 ℃, adding 50g of toluene diisocyanate and 2g of catalyst, 5g of chain extender, heating to 90 ℃ for reaction and timing for 2 hours, adding 6g of latent curing agent XY-3767 and 2g of XY-401, 100g of dimethyl carbonate and 50g of solvent oil, stirring for 0.5h, defoaming and discharging to obtain the single-component polyurethane waterproof paint.
Example 2
5g of polyether polyol (2) with a furan-like structure (180 g, 5g of poly (dimethylphenol) glycol (with a number average molecular weight of 2000 g/mol), 100g of chlorinated paraffin, 100g of kaolin, 200g of calcium carbonate, 200g of talcum powder and 3g of phenyl methyl dimethoxy silane are mixed, dispersed, heated to 100 ℃ for dehydration and timing for 2 hours, cooled to 80 ℃, 46g of toluene diisocyanate, 2g of catalyst and 4g of chain extender are added, heated to 90 ℃ for reaction and timing for 2 hours, 8g of latent curing agent XY-3767 and 4g of XY-401, 100g of dimethyl carbonate and 50g of solvent oil are added, and the mixture is stirred for 0.5 hour for defoaming and discharging to obtain the single-component polyurethane waterproof coating.
Example 3
4g of polyether polyol (3) with a furan-like structure (180 g, 4g of poly (dimethylphenol) dihydric alcohol (with the number average molecular weight of 2000 g/mol), 100g of chlorinated paraffin, 100g of kaolin, 200g of calcium carbonate, 200g of talcum powder, 1g of diphenyl dimethoxy silane and 2g of phenyl trimethoxy silane are mixed, dispersed and heated to 100 ℃ for dehydration and timing for 2 hours, cooled to 80 ℃, 54g of toluene diisocyanate, 2g of catalyst and 4g of chain extender are added, heated to 90 ℃ for reaction and timing for 2 hours, 6g of latent curing agent, 6g of XY-3767, 3g of XY-401, 100g of dimethyl carbonate and 44g of solvent oil are added, and the mixture is stirred for 0.5 hour for defoaming and discharging to obtain the single-component polyurethane waterproof paint.
Comparative example 1
45g of polyether polyol INOVOL F330N, 135g of INOVOL C220, 100g of chlorinated paraffin, 100g of kaolin, 200g of calcium carbonate, 204g of talcum powder and 1g of phenyl triethoxysilane are mixed, dispersed, heated to 100 ℃, dehydrated and timed for 2 hours, cooled to 80 ℃, 50g of toluene diisocyanate, 2g of catalyst and 5g of chain extender are added, heated to 90 ℃ and timed for 2 hours, 6g of latent curing agent XY-3767, 2g of XY-401, 100g of dimethyl carbonate and 50g of solvent oil are added, stirred for 0.5 hour and defoamed, and then the single-component polyurethane waterproof paint is obtained.
Comparative example 2
45g of polyether polyol INOVOL F330N, 135g of INOVOL C220, 4g of poly (dimethylphenol) dihydric alcohol (with the number average molecular weight of 2000 g/mol), 100g of chlorinated paraffin, 100g of kaolin, 200g of calcium carbonate, 202g of talcum powder and 1g of phenyl triethoxysilane are mixed, dispersed, heated to 100 ℃, dehydrated for 2 hours, cooled to 80 ℃, 50g of toluene diisocyanate, 2g of catalyst and 5g of chain extender are added, heated to 90 ℃ for 2 hours, and then 6g of latent curing agent, 2g of XY-3767, 100g of dimethyl carbonate and 50g of solvent oil are added, and the mixture is stirred for 0.5 hour to defoam and discharge to obtain the single-component polyurethane waterproof paint.
Performance test:
(1) The molecular weight and molecular weight distribution of the polyether polyol with the furan-like structure pass through gel permeation chromatography test (Agilent 1260), tetrahydrofuran is taken as a mobile phase, GPC spectra of the polyether polyols (1), (2) and (3) with the furan-like structure are shown in figures 1-3, and the molecular weight and distribution are shown in table 1.
TABLE 1 polyether polyol molecular weight and distribution
From FIGS. 1-3, the synthetic product has no small molecular weight tail, demonstrating that the composite initiator has induced polymerization of alkylene oxide during polymerization.
(2) Infrared spectrograms (Bruce ALPHAII Fourier infrared spectrometer, resolution 2 cm) of furan-like polyether polyol (1), (2) and (3) -1 ) As shown in fig. 4-6.
From FIGS. 4-6, it can be seen that 3480cm appears in each of the IR spectra -1 Is OH stretching vibration peak, 1109cm -1 The polyether polyol was further demonstrated to be successfully prepared as an ether group characteristic peak.
(3) Mechanical properties of polyurethane waterproof paint
The performance of the single-component polyurethane waterproof paint obtained by the implementation was tested by the method disclosed in GB19250-2013 polyurethane waterproof paint, and the results are shown in Table 2.
TABLE 2 mechanical Properties of polyurethane waterproof coating
As can be seen from Table 2, compared with the comparative examples, the tensile strength of the examples is obviously improved, the mechanical properties of the single-component polyurethane waterproof coating are effectively improved, and the invention has wide industrial application prospect.
Claims (10)
1. The single-component polyurethane waterproof coating is characterized by comprising the following raw materials:
polyether polyol with furan-like structure, polydimethyl phenol dihydric alcohol, phenylsilane coupling agent, composite latent curing agent, plasticizer, filler, toluene diisocyanate, catalyst, chain extender and viscosity reducer;
wherein:
the number average molecular weight of the polyether polyol with the furan-like structure is 2000-3000g/mol, and the hydroxyl value is 44-55mgKOH/g;
the polyether polyol with the furan-like structure is obtained by adopting a composite initiator and ring-opening polymerization of alkylene oxide;
the composite initiator is a mixture of polyether polyol with functionality of 2 and number average molecular weight of 400g/mol, isosorbide, polyether polyol with functionality of 3 and number average molecular weight of 500 g/mol.
2. The monocomponent polyurethane waterproof paint of claim 1, wherein the furan-like polyether polyol is obtained by adopting a composite initiator and a bimetallic catalyst to catalyze ring-opening polymerization reaction of alkylene oxide, and the structural formula of the furan-like polyether polyol is shown as follows;
wherein: m is more than or equal to 30 and less than or equal to 45, n is more than or equal to 1 and less than or equal to 5;
the composite initiator is a mixture of polyether polyol with the functionality of 2, the number average molecular weight of 400g/mol, isosorbide, the functionality of 3 and the mass ratio of polyether polyol with the number average molecular weight of 500g/mol of 40-260:29-114:50-75.
3. The one-component polyurethane waterproof paint according to claim 1, wherein the mass ratio of the alkylene oxide to the composite initiator is (6-10): 1.
4. The one-component polyurethane waterproof paint according to claim 2, wherein the amount of the bimetallic catalyst is 100-200 ppm.
5. The one-component polyurethane waterproof paint according to claim 1, wherein the ring-opening polymerization reaction temperature is 130-145 ℃.
6. The one-component polyurethane waterproof paint according to claim 1, wherein the mass ratio of the polydimethyl phenol diol to the polyether polyol with a furan-like structure is (1-3): 100.
7. The single-component polyurethane waterproof paint of claim 1, wherein the phenylsilane coupling agent is one or more of phenyltriethoxysilane, phenylmethyldimethoxysilane, diphenyldimethoxysilane and phenyltrimethoxysilane, and the proportion of the phenyltrimethoxysilane coupling agent in the total amount of the raw materials is 1-3 wt%.
8. The one-component polyurethane waterproof paint according to claim 1, wherein the composite latent curing agent is a mixture of an aliphatic imine-type latent curing agent and an aromatic imine-type latent curing agent.
9. The one-component polyurethane waterproof paint according to claim 8, wherein the mass ratio of the aliphatic imine type latent curing agent to the aromatic imine type latent curing agent is (2-3): 1, and the ratio of the aliphatic imine type latent curing agent to the aromatic imine type latent curing agent is 0.8-1.5wt.% in the total amount of the raw materials.
10. A process for preparing the one-component polyurethane waterproof paint as claimed in any one of claims 1 to 9, comprising the steps of:
and uniformly mixing polyether polyol with a furan-like structure, poly (dimethylphenol) dihydric alcohol, a plasticizer, a filler and a phenylsilane coupling agent, heating for dehydration, cooling, adding toluene diisocyanate, a catalyst and a chain extender, heating for reaction, adding a latent curing agent and a viscosity reducer, stirring, defoaming and discharging to obtain the single-component polyurethane waterproof coating.
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| CN115651524A (en) * | 2022-10-12 | 2023-01-31 | 华南理工大学 | High-strength self-cleaning polyurethane waterproof coating and preparation method thereof |
| CN115677977A (en) * | 2022-12-09 | 2023-02-03 | 山东一诺威新材料有限公司 | Three-dimensional composite polyurethane elastomer and preparation method thereof |
| CN116218349A (en) * | 2022-12-15 | 2023-06-06 | 北京东方雨虹防水技术股份有限公司 | High-strength single-component polyurethane waterproof coating and preparation method thereof |
| WO2023133744A1 (en) * | 2022-01-13 | 2023-07-20 | Henkel Ag & Co. Kgaa | High bio-content polyurethane hot melt adhesive composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023133744A1 (en) * | 2022-01-13 | 2023-07-20 | Henkel Ag & Co. Kgaa | High bio-content polyurethane hot melt adhesive composition |
| CN115651524A (en) * | 2022-10-12 | 2023-01-31 | 华南理工大学 | High-strength self-cleaning polyurethane waterproof coating and preparation method thereof |
| CN115677977A (en) * | 2022-12-09 | 2023-02-03 | 山东一诺威新材料有限公司 | Three-dimensional composite polyurethane elastomer and preparation method thereof |
| CN116218349A (en) * | 2022-12-15 | 2023-06-06 | 北京东方雨虹防水技术股份有限公司 | High-strength single-component polyurethane waterproof coating and preparation method thereof |
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