CN104140518B - A kind of hydrophily one-component water cure polyurethane and preparation method thereof - Google Patents
A kind of hydrophily one-component water cure polyurethane and preparation method thereof Download PDFInfo
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- CN104140518B CN104140518B CN201410350004.2A CN201410350004A CN104140518B CN 104140518 B CN104140518 B CN 104140518B CN 201410350004 A CN201410350004 A CN 201410350004A CN 104140518 B CN104140518 B CN 104140518B
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- hydrophily
- component water
- water cure
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- polyalcohol
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- 229920002635 polyurethane Polymers 0.000 title claims abstract description 34
- 239000004814 polyurethane Substances 0.000 title claims abstract description 34
- 238000009156 water cure Methods 0.000 title claims abstract description 27
- 230000010148 water-pollination Effects 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 25
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 19
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 16
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 16
- 239000012948 isocyanate Substances 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 11
- 239000001294 propane Substances 0.000 claims abstract description 11
- 239000004014 plasticizer Substances 0.000 claims abstract description 10
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 9
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000012653 anionic ring-opening polymerization Methods 0.000 claims abstract description 3
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 3
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims abstract description 3
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 30
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- 238000009835 boiling Methods 0.000 claims description 14
- 150000002148 esters Chemical class 0.000 claims description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 239000003085 diluting agent Substances 0.000 claims description 9
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 8
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 6
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 6
- -1 aliphatic diester Chemical class 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 208000032026 No-Reflow Phenomenon Diseases 0.000 claims description 5
- 206010063837 Reperfusion injury Diseases 0.000 claims description 5
- 238000006073 displacement reaction Methods 0.000 claims description 5
- 238000003828 vacuum filtration Methods 0.000 claims description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 4
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 4
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 4
- SIXWIUJQBBANGK-UHFFFAOYSA-N 4-(4-fluorophenyl)-1h-pyrazol-5-amine Chemical compound N1N=CC(C=2C=CC(F)=CC=2)=C1N SIXWIUJQBBANGK-UHFFFAOYSA-N 0.000 claims description 3
- KBIWNQVZKHSHTI-UHFFFAOYSA-N 4-n,4-n-dimethylbenzene-1,4-diamine;oxalic acid Chemical compound OC(=O)C(O)=O.CN(C)C1=CC=C(N)C=C1 KBIWNQVZKHSHTI-UHFFFAOYSA-N 0.000 claims description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Natural products OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 3
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 3
- 239000012965 benzophenone Substances 0.000 claims description 3
- 239000001110 calcium chloride Substances 0.000 claims description 3
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 3
- 150000002989 phenols Chemical class 0.000 claims description 3
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 2
- 125000003827 glycol group Chemical group 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 239000005416 organic matter Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- CKLJMWTZIZZHCS-UWTATZPHSA-N D-aspartic acid Chemical compound OC(=O)[C@H](N)CC(O)=O CKLJMWTZIZZHCS-UWTATZPHSA-N 0.000 claims 1
- 239000004593 Epoxy Substances 0.000 claims 1
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 claims 1
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 150000002576 ketones Chemical class 0.000 claims 1
- 150000002895 organic esters Chemical class 0.000 claims 1
- 239000007800 oxidant agent Substances 0.000 claims 1
- 230000001590 oxidative effect Effects 0.000 claims 1
- 229910052698 phosphorus Inorganic materials 0.000 claims 1
- 239000011574 phosphorus Substances 0.000 claims 1
- 230000005855 radiation Effects 0.000 claims 1
- 229940116351 sebacate Drugs 0.000 claims 1
- 239000007787 solid Substances 0.000 abstract description 7
- 239000002253 acid Substances 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 150000007513 acids Chemical class 0.000 abstract description 2
- 238000000034 method Methods 0.000 abstract description 2
- 238000004162 soil erosion Methods 0.000 abstract description 2
- 238000003860 storage Methods 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 8
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 4
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- 239000006096 absorbing agent Substances 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 2
- ACPFCDQHTJDRLZ-UHFFFAOYSA-N O1CCOCC1.C(CCCCCCCCC(=O)O)(=O)O Chemical compound O1CCOCC1.C(CCCCCCCCC(=O)O)(=O)O ACPFCDQHTJDRLZ-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 229940124543 ultraviolet light absorber Drugs 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- 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
- C08G18/4833—Polyethers containing oxyethylene units
- C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
-
- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
-
- 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
- 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
- C08G65/2648—Alkali metals or compounds thereof
Abstract
The present invention provides a kind of hydrophily one-component water cure polyurethane and preparation method thereof, using anionic ring-opening polymerization means, using polyethylene glycol as starting dihydric alcohol, under the conditions of existing for KOH, ring-opening polymerisation is carried out with expoxy propane, by adjusting molecular weight polyethylene glycol, polyethylene glycol addition and expoxy propane addition, polyalcohol of the synthesis with different molecular weight and hydrophobe chain length;In the presence of catalyst, polyalcohol and isocyanates are reacted, add appropriate plasticizer, antioxidant, ultra-violet absorber, prepare the base polyurethane prepolymer for use as that end group is NCO group;Performed polymer is mixed with water with certain proportion, obtains one-component water cure polyurethane.The inventive method is simple, it is easy to operate, products obtained therefrom solid content is high, curing rate is fast, moisture-holding capacity is high, storage stability is good, and with good pliability, weatherability, resistance to acids and bases, has broad application prospects controlling soil erosion and preparing waterproof material etc..
Description
(1) technical field
The present invention relates to a kind of polyurethane, belongs to material and chemical field, specifically a kind of hydrophily one-component water
Solidify polyurethane and preparation method thereof.
(2) background technology
Film has good ornamental, excellent caking property, rub resistance, high resiliency and gloss after urethane cures
Degree, it is deep by market and consumers in general's pro-gaze.At present using it is more be solvent borne polyurethane.In recent years because people are to environment
The needs of protection, the polyurethane of low VOC (VOC) content increasingly cause the extensive concern of people.Low VOC contains
The improvement of weight polyurethane performance is mainly reflected in following two aspects:1) it is molten to reduce to greatest extent to improve polyurethane solid content
Agent dosage, reduce VOC content;2) free isocyanate content of monomer in polyurethane, exploitation high-performance, nontoxic poly- ammonia are reduced
Ester.
In recent years, the research of one-component water cure polyurethane becomes increasingly active, and water cure polyurethane is using water as curing agent, construction
It is convenient and nontoxic, tasteless, pollution-free, the excellent physical and mechanical properties of solvent borne polyurethane had both been maintained, while required solvent is few,
Therefore the volatilization of solvent substantially reduces, and the influence to environment is small, more environmentally friendly.But one-component water cure polyurethane solid content is low,
Hardening time is long, moisture-holding capacity is low.
(3) content of the invention
The technical assignment of the present invention is in view of the shortcomings of the prior art, there is provided a kind of hydrophily one-component water cure polyurethane
Preparation method, solve the problems, such as that one-component water cure polyurethane solid content is low, curing rate is slow, moisture-holding capacity is low.
The technical solution adopted by the present invention is:
A kind of hydrophily one-component water cure polyurethane, using anionic ring-opening polymerization means, using polyethylene glycol as rising
Beginning dihydric alcohol, under the conditions of existing for KOH, ring-opening polymerisation is carried out with expoxy propane, by adjusting molecular weight polyethylene glycol, poly- second
Glycol addition and expoxy propane addition, polyalcohol of the synthesis with different molecular weight and hydrophobe chain length;Urging
In the presence of agent, the polyalcohol prepared and isocyanates are reacted, add appropriate plasticizer, antioxidant, ultraviolet
Light absorbers mix, and are down to room temperature, diluent is added after discharging, prepare polyurethane prepolymer of the end group for-NCO group
Body;Base polyurethane prepolymer for use as and water are reacted according to mass fraction 1: 1-1: 35, obtain the poly- ammonia of hydrophily one-component water cure
Ester;
The base polyurethane prepolymer for use as raw material composition and each component mass fraction are as follows:
Polyethylene glycol:20-60 parts;KOH:0.2-5 parts;Expoxy propane:3-20 parts;Catalyst:0.2-1 parts;Isocyanates:
0.6-25 parts;Plasticizer:0-2 parts;Antioxidant:1-5 parts;Ultra-violet absorber:0.1-1 parts;Diluent:4-18 parts.
Wherein described molecular weight polyethylene glycol scope is 1000-10500.
Wherein described catalyst is one or both of triethylamine, dibutyl tin laurate.
Wherein described isocyanates is one or both of toluene di-isocyanate(TDI), '-diphenylmethane diisocyanate.
Wherein described plasticizer is the aliphatic diester of triethylene glycol or tetraethylene glycol, diisooctyl phthalate, the last of the ten Heavenly stems two
One or more in acid dialkyl ester, ethanedioic acid dialkyl ester, tricresyl phosphate organic ester.
Wherein described antioxidant is the one or more in phenols, phosphine, esters organic matter.
Wherein described ultra-violet absorber is made up of the BTA of 0-80 parts and the benzophenone of 20-100 parts.
Wherein described diluent is one or both of acetone, butanone.
A kind of preparation method of hydrophily one-component water cure polyurethane, including step are as follows:
1) each component is weighed according to above-mentioned mass fraction;
2) polyethylene glycol and KOH are added in four-hole boiling flask, vacuum be 0.1MPa, temperature be 100-120 DEG C of oil
1-3h is dehydrated under the conditions of bath, is cooled to 70 DEG C -90 DEG C;
3) condenser pipe, thermometer and nitrogen interface are linked into four-hole boiling flask, vacuumized and nitrogen displacement 3-5 times, with
Eliminate the air in four-hole boiling flask;Keep this temperature-resistant, under conditions of nitrogen protection, be added dropwise using constant pressure funnel
The expoxy propane of mass fraction is stated, continues reaction after being added dropwise until no reflow phenomenon, is cooled to room temperature, obtains thick polyalcohol;
4) dichloromethane is added into the thick polyalcohol of step 3), using Vacuum filtration device, filter paper is replaced with diatomite
To remove KOH, regulation pH is 5-6, and adds drier, is concentrated to give polyalcohol;
5) polyalcohol for obtaining step 4) be added to equipped with thermometer, electric agitator three-necked flask in, raise temperature
To 50-75 DEG C, catalyst, the isocyanates of above-mentioned mass fraction are added, 1.5-3h is reacted, adds the increasing of above-mentioned mass fraction
Mould agent, antioxidant, ultra-violet absorber, continue to react 1-2h, reduce temperature to room temperature, add diluent, obtain end group for-
The base polyurethane prepolymer for use as of NCO group;
6) base polyurethane prepolymer for use as and water prepared step 5) is reacted according to mass fraction 1: 1-1: 35, is obtained hydrophilic
Property one-component water cure polyurethane;
Drier wherein described in step 4) is magnesium sulfate, the one or more in calcium chloride, magnesium chloride.
The inventive method is simple, easy to operate, and products obtained therefrom solid content is mixed with water in 80%-89%, moisture-holding capacity >=35
Rear curing time is 30s-1800s, and has good pliability, weatherability, resistance to acids and bases and storage stability, is being controlled
Manage soil erosion and prepare waterproof material etc. and have broad application prospects.,
Brief description of the drawings
Fig. 1 is the FT-IR figures of base polyurethane prepolymer for use as in the embodiment of the present invention 1.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention will be further described.
The hydrophily one-component water cure urethane raw of the present invention forms:Polyethylene glycol, KOH, expoxy propane, catalysis
Agent, isocyanates, plasticizer, antioxidant, ultra-violet absorber, diluent, drier and water.
Wherein, plasticizer is the aliphatic diester of triethylene glycol or tetraethylene glycol, diisooctyl phthalate, decanedioic acid dioxane
One or more in base ester, ethanedioic acid dialkyl ester, tricresyl phosphate organic ester;Antioxidant is that phenols, phosphine, esters etc. are organic
One or more in thing;Ultra-violet absorber is made up of the BTA of 0-80 parts and the benzophenone of 20-100 parts.
Prepared using the FT-IR types infrared spectrometers of the Avatar 370 test present invention of Nicolet companies of U.S. production
The FT-IR infrared spectrums of base polyurethane prepolymer for use as.
Embodiment 1:
1) 20.12g polyethylene glycol 2000s, 0.95g KOH are added in four-hole boiling flask, are 0.1MPa, temperature in vacuum
Spend to be dehydrated 2h under the conditions of 110 DEG C of oil baths, be cooled to 85 DEG C;
2) condenser pipe, thermometer and nitrogen interface are linked into four-hole boiling flask, vacuumized and nitrogen displacement 3 times, to eliminate
Air in four-hole boiling flask;Keep this temperature-resistant, under conditions of nitrogen protection, 5.83g is added dropwise using constant pressure funnel
Expoxy propane, continue reaction after being added dropwise until no reflow phenomenon, is cooled to room temperature, obtains thick polyalcohol;
3) 100mL dichloromethane is added into the thick polyalcohol of step 3), using Vacuum filtration device, with diatomite generation
For filter paper to remove KOH, regulation pH is 5, and adds drier magnesium sulfate, is concentrated to give polyalcohol;
4) polyalcohol for obtaining step 3) be added to equipped with thermometer, electric agitator three-necked flask in, raise temperature
To under conditions of 55 DEG C, 0.81g Triethylamine catalysts, 3.52g toluene di-isocyanate(TDI)s are added, reacts 2h, adds 1.15g increasings
Agent, 1.45g antioxidants, 0.75g ultra-violet absorbers are moulded, insulation reaction 2h, temperature is reduced to room temperature, adds 6mL acetone, obtain
Base polyurethane prepolymer for use as to end group for-NCO group;
5) base polyurethane prepolymer for use as 5.00g obtained by weighing step 4), is mixed with 100mL water, and hydrophily one-component water is made and consolidates
Change polyurethane.It is well mixed using magnetic stirring apparatus, pours into mould film forming, tests its performance, the results listed in the following table:
Sequence number | Test event | Test result |
1 | Tensile strength/MPa | 20.87 |
2 | Elongation at break/% | 324.23 |
3 | Solid content/% | 86.56 |
4 | Surface drying timea/min | 8.5 |
5 | Do solid work the timea/h | 9.5 |
a20 DEG C of test temperature
Embodiment 2:
1) 20.00g cetomacrogol 1000s, 0.20g KOH are added in four-hole boiling flask, are 0.1MPa, temperature in vacuum
Spend to be dehydrated 1h under the conditions of 100 DEG C of oil baths, be cooled to 70 DEG C;
2) condenser pipe, thermometer and nitrogen interface are linked into four-hole boiling flask, vacuumized and nitrogen displacement 4 times, to eliminate
Air in four-hole boiling flask;Keep this temperature-resistant, under conditions of nitrogen protection, 3.00g is slowly added dropwise in constant pressure funnel
Expoxy propane, continue reaction after being added dropwise until no reflow phenomenon, is cooled to room temperature, obtains thick polyalcohol;
3) 80mL dichloromethane is added into the thick polyalcohol of step 2), using Vacuum filtration device, uses diatom
Soil replaces filter paper to remove KOH, and regulation pH is 5, and adds drier calcium chloride, is concentrated to give polyalcohol;
4) polyalcohol for obtaining step 3) be added to equipped with thermometer, electric agitator three-necked flask in, raise temperature
To under conditions of 50 DEG C, 0.20g dibutyltin dilaurate catalysts, 0.60g '-diphenylmethane diisocyanates, reaction are added
1.5h, 1.00g antioxidants, 0.10g ultra-violet absorbers are added, insulation reaction 1h, temperature is reduced to room temperature, adds 4mL
Butanone, obtain base polyurethane prepolymer for use as of the end group for-NCO group;
5) base polyurethane prepolymer for use as 10.00g obtained by weighing step 4), is mixed with 10mL water, and hydrophily one-component water is made and consolidates
Change polyurethane.
Embodiment 3:
1) 60.00g polyethylene glycol 10500,5.00g KOH are added in four-hole boiling flask, are 0.1MPa, temperature in vacuum
Spend to be dehydrated 3h under the conditions of 120 DEG C of oil baths, be cooled to 90 DEG C;
2) condenser pipe, thermometer and nitrogen interface are linked into four-hole boiling flask, vacuumized and nitrogen displacement 5 times, to eliminate
Air in four-hole boiling flask;Keep this temperature-resistant, under conditions of nitrogen protection, 20.00g is slowly added dropwise in constant pressure funnel
Expoxy propane, continue reaction after being added dropwise until no reflow phenomenon, is cooled to room temperature, obtains thick polyalcohol;
3) 120mL dichloromethane is added into the thick polyalcohol of step 2), using Vacuum filtration device, with diatomite generation
For filter paper to remove KOH, regulation pH is 6, and adds drier magnesium sulfate, magnesium chloride, is concentrated to give polyalcohol;
4) polyalcohol for obtaining step 3) be added to equipped with thermometer, electric agitator three-necked flask in, raise temperature
To under conditions of 75 DEG C, mixed catalyst, the 15.00g of 0.40g triethylamines and 0.60g dibutyl tin laurates composition are added
The mixture of '-diphenylmethane diisocyanate and 10.00g '-diphenylmethane diisocyanates composition, reacts 3h, adds 2.00g increasings
Agent, 5.00g antioxidants, 1.00g ultra-violet absorbers are moulded, insulation reaction 1.5h, temperature is reduced to room temperature, adds 10mL acetone
With 8mL butanone, base polyurethane prepolymer for use as of the end group for-NCO group is obtained;
5) base polyurethane prepolymer for use as 1.00g obtained by weighing step 4), is mixed with 35mL water, and hydrophily one-component water cure is made
Polyurethane.
Claims (10)
1. a kind of hydrophily one-component water cure polyurethane, it is characterised in that using anionic ring-opening polymerization means, with poly- second two
Alcohol under the conditions of existing for KOH, carries out ring-opening polymerisation, by adjusting polyethylene glycol point as starting dihydric alcohol with expoxy propane
Son amount, polyethylene glycol addition and expoxy propane addition, synthesis are more with different molecular weight and hydrophobe chain length
First alcohol;In the presence of catalyst, the polyalcohol prepared and isocyanates are reacted, add appropriate plasticizer, antioxygen
Agent, ultra-violet absorber, room temperature is down to, diluent is added after discharging, prepare polyurethane prepolymer of the end group for-NCO group
Body;Base polyurethane prepolymer for use as and water are reacted according to mass fraction 1: 1-1: 35, obtain the poly- ammonia of hydrophily one-component water cure
Ester;
The raw material composition and each component mass fraction of the base polyurethane prepolymer for use as are as follows:
Polyethylene glycol:20-60 parts;KOH:0.2-5 parts;Expoxy propane:3-20 parts;Catalyst:0.2-1 parts;Isocyanates:0.6-
25 parts;Plasticizer:0-2 parts;Antioxidant:1-5 parts;Ultra-violet absorber:0.1-1 parts;Diluent:4-18 parts.
2. hydrophily one-component water cure polyurethane according to claim 1, it is characterised in that described polyethylene glycol point
Son amount scope is 1000-10500.
3. hydrophily one-component water cure polyurethane according to claim 1, it is characterised in that described catalyst is three
One or both of ethamine, dibutyl tin laurate.
4. hydrophily one-component water cure polyurethane according to claim 1, it is characterised in that described isocyanates is
One or both of toluene di-isocyanate(TDI), '-diphenylmethane diisocyanate.
5. hydrophily one-component water cure polyurethane according to claim 1, it is characterised in that described plasticizer is three
The aliphatic diester of glycol or tetraethylene glycol, diisooctyl phthalate, DAS di alkyl sebacate, ethanedioic acid dialkyl ester, phosphorus
One or more in sour three organic esters.
6. hydrophily one-component water cure polyurethane according to claim 1, it is characterised in that described antioxidant is
One or more in phenols, phosphine, esters organic matter.
7. hydrophily one-component water cure polyurethane according to claim 1, it is characterised in that described ultraviolet radiation absorption
Agent is made up of the BTA of 0-80 parts and the benzophenone of 20-100 parts.
8. hydrophily one-component water cure polyurethane according to claim 1, it is characterised in that described diluent is third
One or both of ketone, butanone.
9. a kind of preparation method of hydrophily one-component water cure polyurethane, it is characterised in that comprise the following steps:
1) each component is weighed according to mass fraction as defined in any one of claim 1-8;
2) polyethylene glycol and KOH are added in four-hole boiling flask, vacuum be 0.1MPa, temperature be 100-120 DEG C of oil bath bar
1-3h is dehydrated under part, is cooled to 70 DEG C -90 DEG C;
3) condenser pipe, thermometer and nitrogen interface are linked into four-hole boiling flask, vacuumized and nitrogen displacement 3-5 times, to eliminate four
Air in mouth flask;Keep this temperature-resistant, under conditions of nitrogen protection, epoxy third is added dropwise using constant pressure funnel
Alkane, continue to react after being added dropwise, until no reflow phenomenon, is cooled to room temperature, obtains thick polyalcohol;
4) dichloromethane is added into the thick polyalcohol of step 3), using Vacuum filtration device, replaces filter paper to remove with diatomite
KOH, regulation pH is 5-6, and adds drier, is concentrated to give polyalcohol;
5) by the polyalcohol in step 4) be added to equipped with thermometer, electric agitator three-necked flask in, rise temperature is to 50-75
DEG C, catalyst, the isocyanates of above-mentioned mass fraction are added, reacts 1.5-3h, the plasticizer of above-mentioned mass fraction is added, resists
Oxidant, ultra-violet absorber, continue to react 1-2h, reduce temperature to room temperature, add diluent, obtain end group as-NCO group
Base polyurethane prepolymer for use as;
6) base polyurethane prepolymer for use as and water prepared step 5) is reacted according to mass fraction 1: 1-1: 35, obtains hydrophily list
Component water cure polyurethane.
10. the preparation method of hydrophily one-component water cure polyurethane according to claim 9, it is characterised in that described
Drier be magnesium sulfate, calcium chloride, the one or more in magnesium chloride.
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CN103483547A (en) * | 2013-09-30 | 2014-01-01 | 山东省科学院新材料研究所 | Moisture-curing temperature-sensitive waterproof and moisture-permeable polyurethane and preparation method thereof |
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CN103483547A (en) * | 2013-09-30 | 2014-01-01 | 山东省科学院新材料研究所 | Moisture-curing temperature-sensitive waterproof and moisture-permeable polyurethane and preparation method thereof |
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