CN103739811A - Waterborne polyurethane and preparation method thereof - Google Patents
Waterborne polyurethane and preparation method thereof Download PDFInfo
- Publication number
- CN103739811A CN103739811A CN201310698814.2A CN201310698814A CN103739811A CN 103739811 A CN103739811 A CN 103739811A CN 201310698814 A CN201310698814 A CN 201310698814A CN 103739811 A CN103739811 A CN 103739811A
- Authority
- CN
- China
- Prior art keywords
- aqueous polyurethane
- weight part
- siloxanes
- polyisocyanates
- water
- 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
- 239000004814 polyurethane Substances 0.000 title claims abstract description 44
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- -1 polyamino-siloxane Polymers 0.000 claims abstract description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 16
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 16
- 239000004970 Chain extender Substances 0.000 claims abstract description 15
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 15
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 13
- 229920000570 polyether Polymers 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 24
- 229910019142 PO4 Inorganic materials 0.000 claims description 16
- 239000010452 phosphate Substances 0.000 claims description 16
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 15
- 229920001296 polysiloxane Polymers 0.000 claims description 13
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 229920000642 polymer Polymers 0.000 claims description 8
- DNPNFYJXUGCNNC-UHFFFAOYSA-N 4-hydroxy-2-(hydroxymethyl)butanoic acid Chemical compound OCCC(CO)C(O)=O DNPNFYJXUGCNNC-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000013019 agitation Methods 0.000 claims description 5
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical group OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims description 4
- 238000006386 neutralization reaction Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- OXQGTIUCKGYOAA-UHFFFAOYSA-N 2-Ethylbutanoic acid Chemical compound CCC(CC)C(O)=O OXQGTIUCKGYOAA-UHFFFAOYSA-N 0.000 claims description 3
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 229920001451 polypropylene glycol Polymers 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- VVORZJSSSMSZJQ-UHFFFAOYSA-N 2-ethyl-4,4-dihydroxybutanoic acid Chemical compound CCC(C(O)=O)CC(O)O VVORZJSSSMSZJQ-UHFFFAOYSA-N 0.000 claims description 2
- AWKFZNCALGANRZ-UHFFFAOYSA-N 4,4-dihydroxy-2-methylbutanoic acid Chemical compound OC(=O)C(C)CC(O)O AWKFZNCALGANRZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- DJMIKAGANCZWLL-UHFFFAOYSA-N dihydroxy hydrogen phosphate Chemical group OOP(O)(=O)OO DJMIKAGANCZWLL-UHFFFAOYSA-N 0.000 claims description 2
- 150000002009 diols Chemical class 0.000 claims description 2
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 abstract description 5
- 229920005862 polyol Polymers 0.000 abstract description 4
- 150000003077 polyols Chemical class 0.000 abstract description 4
- 230000035699 permeability Effects 0.000 abstract description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 28
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 14
- 239000000463 material Substances 0.000 description 12
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 10
- 239000000523 sample Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 239000000839 emulsion Substances 0.000 description 7
- 239000003063 flame retardant Substances 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 6
- 239000002023 wood Substances 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 5
- 235000011194 food seasoning agent Nutrition 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000013517 stratification Methods 0.000 description 4
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- UXCDUFKZSUBXGM-UHFFFAOYSA-N phosphoric tribromide Chemical compound BrP(Br)(Br)=O UXCDUFKZSUBXGM-UHFFFAOYSA-N 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000010276 construction Methods 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 239000008393 encapsulating agent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000011527 polyurethane coating Substances 0.000 description 2
- 230000010076 replication Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000009423 ventilation Methods 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- RWLALWYNXFYRGW-UHFFFAOYSA-N 2-Ethyl-1,3-hexanediol Chemical compound CCCC(O)C(CC)CO RWLALWYNXFYRGW-UHFFFAOYSA-N 0.000 description 1
- GNYUQIKGCJOIOO-UHFFFAOYSA-N 3-hydroxy-2-(2-hydroxyethyl)butanoic acid Chemical compound CC(O)C(C(O)=O)CCO GNYUQIKGCJOIOO-UHFFFAOYSA-N 0.000 description 1
- 235000018185 Betula X alpestris Nutrition 0.000 description 1
- 235000018212 Betula X uliginosa Nutrition 0.000 description 1
- 239000008589 Cortex Fraxini Substances 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000001828 Gelatine Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- MJEMIOXXNCZZFK-UHFFFAOYSA-N ethylone Chemical compound CCNC(C)C(=O)C1=CC=C2OCOC2=C1 MJEMIOXXNCZZFK-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000035479 physiological effects, processes and functions Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
- 230000003075 superhydrophobic effect Effects 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 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
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation 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
- C08G18/08—Processes
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
- C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
-
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3893—Low-molecular-weight compounds having heteroatoms other than oxygen containing silicon
-
- 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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
-
- 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
- C08G18/61—Polysiloxanes
-
- 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
- C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
Abstract
The invention provides waterborne polyurethane and a preparation method thereof. The waterborne polyurethane is characterized in that the waterborne polyurethane is synthesized from raw materials of polyether polyol, polyisocyanate, an internal emulsifier, polyamino-siloxane, a chain extender and water. The waterborne polyurethane has high air permeability with self-cleaning and self-flame-retardant functions.
Description
Technical field
The present invention relates to a kind of aqueous polyurethane and preparation method thereof.
Background technology
Since two thousand six, construction timber consumption is the trend that continues rising both at home and abroad, and construction industry becomes the principal market of timber industry product.Along with domestic and international resident to life demand from physiology aspects such as basic existence and inhabitations, rise to health and the spirit level of observing and learn from real life, particularly brought up to and required to have pure and fresh, graceful, environmental protection, natural living environment, green building material, it is day by day urgent that especially outdoor residential log cabin and leisure wood build the demand of building.But timber is in process dry and that use, and due to the ununiformity that each position moisture of the formed timber of microtexture difference moves and evaporates, end cracking very easily appears in timber, and impact is used.The conventional method that prevents end check is coating at present, with water-proof material, processes the surface of timber, and the infiltration of retardance wood surface moisture, reaches unanimity the rate of water migration of its inside and outside.
The at present domestic water-proof coating generally using has gelatine (being commonly called as glue), paraffin, pitch and synthesis of polyurethane coating etc.But all exist certain defect:
(1) conventional synthesis of polyurethane layer is almost solvent-borne type product, contains the organic solvents such as poisonous and hazardous aromatic hydrocarbon, ketone, and environment and health of human body are caused to very large harm.
(2) paraffin and pitch and most synthesis of polyurethane water-proof breathable properties are poor, are not suitable for rainy open air use, and poor because of ventilation property, and steam cannot be discharged in woodwork, causes timber crack and coating shedding.
(3) most products do not have anti-flaming function, or long-term flame retardant effect is poor, and safety in utilization reduces, and the use range of woodwork is limited to.
Summary of the invention
The object of this invention is to provide and a kind ofly there is automatically cleaning and from ventilative water soluble polyurethane wood anticracking encapsulant of the height of anti-flaming function and preparation method thereof.
In order to achieve the above object, the invention provides a kind of aqueous polyurethane, it is characterized in that, by the raw material that comprises polyether glycol, polyisocyanates, internal emulsifying agent, polyamino siloxanes, chainextender and water is synthetic, obtain.
Preferably, described polyamino siloxanes is one or more in diamino siloxanes, diamino polysiloxane, triamino siloxanes and triamino siloxanes.
More preferably, described polyamino siloxanes is triamino siloxanes or triamino polysiloxane.
Preferably, described polyisocyanates is TDI, MD1 or PAPI.
Preferably, in described polysiloxane segment, at least contain 2 Siliciumatoms.
Preferably, described polyether glycol is one or more in polyoxypropyleneglycol, polyoxytrimethylene triol and polytetrahydrofuran diol.
The number-average molecular weight of described polyether glycol is for example 200～8000, is preferably 300～5000, and hydroxyl equivalent is for example 80～5000, is preferably 100～3000.
Described internal emulsifying agent refers to the material that has 2 hydroxyls and have carboxyl.Preferably, described internal emulsifying agent is 2,2-dimethylolpropionic acid, 2,2-dimethylol propionic acid, 2,2-dihydroxy ethyl butyric acid, 2,2-dihydroxy ethyl propionic acid, 2,3-dimethylolpropionic acid, 2,3-dimethylol propionic acid, one or more in 2,3-dihydroxy ethyl butyric acid and 2,3-dihydroxy ethyl propionic acid.
Described internal emulsifying agent also can select to contain amino material.Preferably, described internal emulsifying agent is methylol amine methylbutyric, ethylol amine ethyl butyric acid, one or more in diamines methylbutyric and diamines ethyl butyric acid.
Described chainextender is the material that contains 2 groups that react with isocyanic ester.
Preferably, described chainextender is polyhydroxy phosphate.
Polyhydroxy phosphate is as chainextender: on the one hand; pass through chain extending reaction; in molecular structure inside, introduced organic phosphate flame-retardant group; in coating, meet in the process of fiery heat, can form phosphoric acid, phosphoric acid can absorb heat; as dewatering agent, promote into charcoal; and can form the glass protective layer of one deck, thereby fire-retardant function is played in blocking oxygen diffusion and thermal conduction.Owing to being the fire-retardant group of introducing at intramolecule, so this flame retardant properties is permanent, be different from common additional fire retardant.On the other hand, from polyhydroxy phosphate structural analysis, its one end is lipophilic group, and the other end is hydrophilic radical, is both sexes chainextender, can realize the technique of performed polymer chain extension in water, thereby does not need additional any solvent, and product is environmental protection more.
More preferably, described polyhydroxy phosphate has following structure:
In above formula, R
1, R
2, R
3in at least contain an oh group, R
1, R
3, R
3independently represent alcohol straight or branched, that saturated or undersaturated alcohol, alkyl, epoxy compounds or open loop of epoxy compound form.
Described polyhydroxy phosphate is reacted and is obtained by polyol or oxy-compound and phosphoric acid agent.Phosphorus wherein comes from Vanadium Pentoxide in FLAKES, Tripyrophosphoric acid, phosphoric acid, Phosphorus Oxychloride, phosphorus oxybromide etc.Vanadium Pentoxide in FLAKES, Tripyrophosphoric acid, phosphoric acid, Phosphorus Oxychloride, phosphorus oxybromide can be called as phosphoric acid agent.
In order to reduce the generation of acidic substance, described phosphoric acid agent is preferably Vanadium Pentoxide in FLAKES, Tripyrophosphoric acid or phosphoric acid.
In order to obtain the more polyhydroxy phosphate of high yield, described phosphoric acid agent is preferably Phosphorus Oxychloride or phosphorus oxybromide, more preferably Phosphorus Oxychloride.
While using phosphoric acid agent, if phosphoric acid agent is excessive, due to the generation of former phosphoric acid, can have a strong impact on the stability of product, in production process, need to remove the technique of phosphoric acid agent.When the present invention prepares polyhydroxy phosphate, adopt polyol excessive.
As a kind of preferred, in the prior art, the hydroxyl of polyhydroxy phosphate is distributed in the R in above formula
1, R
2, R
3in, particularly, as 2 hydroxyls are distributed in R
1, R
2in, be in the process of chain extension, phosphorus atom is called a part for main chain in polymkeric substance, due to the hydrolysis problem of phosphoric acid ester and the mechanical property of P-O key poor, the mechanical properties decrease that causes aqueous polyurethane, the hydrolysis of phosphoric acid simultaneously has also further reduced mechanical property and water resistance and the weathering resistance of aqueous polyurethane.So the poly-hydroxy of the polyhydroxy phosphate in the present invention is distributed in R
1or R
2or R
3in, so the phosphoric acid ester in the aqueous polyurethane making is side chain, this does not affect the performance of main chain, meanwhile, because phosphoric acid ester has good hydrophilicity, can be conducive to obtain the aqueous polyurethane with better permeability.
Aspect flame retardant properties, aqueous polyurethane of the present invention, for the encapsulant of timber, makes wood surface have fine hydrophobicity, does not lose permeability simultaneously, can prevent timber crack.
More preferably, described polyhydroxy phosphate is dihydroxyl phosphoric acid ester, tetrahydroxy phosphoric acid ester or hexahydroxy-phosphoric acid ester, R
1, R
2and R
3in at least one contains dihydroxyl structure.
Preferably, described polyol is trihydroxy-compound, and described trihydroxy-compound has following structure: CH[(CH
2)
moH]
3or CH[(CH
2)
mo (CH2)
noH]
3, wherein, m and n are more than or equal to 1 integer.
The present invention also provides a kind of preparation method of aqueous polyurethane, it is characterized in that, concrete steps comprise:
The first step: polyether glycol 100 weight parts, polyisocyanates 120-140 weight part and internal emulsifying agent 3-5 weight part are uniformly mixed under 7-10 degree Celsius, under agitation add polyamino siloxanes 2-6 weight part to react, form side chain containing the compound of polysiloxane; Or, polyether glycol 100 weight parts and polyisocyanates 120-140 weight part are uniformly mixed under 7-10 degree Celsius, under agitation add polyamino siloxanes 2-6 weight part to react, form side chain containing the compound of polysiloxane, then add internal emulsifying agent 3-5 weight part;
Second step: add polyisocyanates 10-50 weight part after reacting completely, be warming up to 50-80 ℃ of reaction and obtain performed polymer;
The 3rd step: chainextender 14-16 weight part is mixed with water 350-450 weight part, performed polymer is slowly added in the water that contains chainextender of gained, then add triethylamine neutralization, obtain aqueous polyurethane.
Preferably, the reaction times of the described the first step is 0.5-3 hour, and the reaction times of described second step is 2-6 hour.
Preferably, described side chain is expressed from the next containing the structure of the compound of polysiloxane:
Wherein, A represents polyisocyanates, and R1 is C-C segment and/or C-O segment; In R2, R3, R4, one of them is polysiloxane segment, and other two independently represent hydrogen atom, alkyl or aralkyl.
Preferably, described aqueous polyurethane at least comprises the side chain containing polysiloxane, and the main chain that contains phosphoric acid ester or side chain.
Due to reactivity ratio's hydroxyl of amino and isocyanic ester and isocyanic ester by force, so the present invention adopts under lower temperature conditions, inhibition hydroxyl reacts with isocyanic ester, so that contain the polysiloxane-grafted in polyisocyanates of amino, obtain the performed polymer that contains polysiloxane, contains a plurality of isocyanate groups.
Compared with prior art, the invention has the beneficial effects as follows:
1, the aqueous polyurethane that prepared by the present invention, need not add other auxiliary agents, can be used for wood sealer.
2, the present invention introduces in hydrophobic hard section of part the siloxane groups that side is hung.The Si-O-Si hydrophobic grouping of siloxanes because containing repetition, surface can be extremely low, forms a thermodynamic unstable system in aqueous emulsion of polyurethane.In the process volatilizing of filming, along with the evaporation of moisture, the medium in polyaminoester emulsion constantly changes, surperficial siloxanes side chaining section that can be extremely low trends towards to surface transport, contact with air, two-phase produces relatively mobile, and siloxanes forms super-hydrophobic structure in coatingsurface enrichment.Can give polyurethane coating good self-cleaning function.
3, the synthetic urethane of the present invention also has considerable part hydrophilic soft section, when outside air temperature is higher, humidity is when lower, these hydrophilic radicals can be caught the water vapour distributing in timber with the form of hydrogen bond, due to the thermal motion of polyurethane macromolecular segment, form instantaneous hole, add the promotion of inside and outside water vapor pressure, water vapour is from the high side " transmission " of vapour pressure to opposite side, vice versa, plays ventilative function, to regulate the balance of inside and outside humidity.Meanwhile, due to water resisting property and the larger film tension force of material self of hard section, top coat has water-repellancy, can prevent the erosion of extraneous rainwater etc.
Embodiment
For the present invention is become apparent, hereby with preferred embodiment, be described in detail below.
Embodiment 1-4
Embodiment 1-4 adopts respectively following formula to prepare polyhydroxy phosphate:
Unit: weight part
| ? | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Phosphorus oxychloride | 153 | 153 | 153 | 153 |
| Propylene glycol | 124 | ? | ? | ? |
| Glycerol | ? | ? | 92 | ? |
| Propyl carbinol | 1200 | 1200 | 1200 | 1200 |
| 2-ethyl-1,3-hexylene glycol | ? | 292 | ? | ? |
| TriMethylolPropane(TMP) | ? | ? | ? | 134 |
The preparation technology of embodiment 1-4 is:
1) esterification: by proportioning, phosphorus oxychloride is put in reactor to the protection of helium injection gas.In chuck, pass into water coolant, when material in reactor temperature reaches after 25 ℃, start to drip dibasic alcohol or trivalent alcohol.Keep temperature of reaction: 50 ℃; Stir speed (S.S.): 100 revs/min.After dripping off, start to add propyl carbinol, insulation reaction 2 hours.The HCl gas generating, by three grades of resorbers, water absorbs, and makes the hydrochloric acid of mass concentration 30%.
2) distillation: material is transferred in still kettle, steamed excessive propyl carbinol, the alcohol amount that metering steams, while reaching theoretical amount, distillation finishes.
3) alkali neutralization: distillation finishes, stirs, and chuck leads to cold oil, circulating cooling to 40 ℃.Slowly adding concentration is 50% sodium hydroxide solution, keeps temperature lower than 60 ℃, and 75 revs/min of mixing speed, until pH=6.7.
4) distillation dehydration: in vacuum tightness: 0.1MPa, temperature: under the condition of 170 ℃, steam moisture to water content and be less than 0.5% for qualified.
5) filter: be cooled to 70 ℃, with plate-and-frame filter press, filter out salt, obtain polyhydroxy phosphate.
Embodiment 5-12
The aqueous polyurethane of embodiment 5-12, obtains by the raw material that comprises polyether glycol, polyisocyanates, internal emulsifying agent, polyamino siloxanes, chainextender and water is synthetic, and each proportioning raw materials is as follows:
Unit: weight part
Wherein, polyoxypropyleneglycol number-average molecular weight 2000; Polyoxytrimethylene triol number-average molecular weight 1500;
According to above-mentioned formula, the technique of preparing aqueous polyurethane is:
The first step: 160% polyisocyanates and internal emulsifying agent of polyether glycol, polyether glycol weight part are uniformly mixed under 8 degrees Celsius;
Second step: under agitation slowly add polyamino siloxanes to react, form side chain containing the compound of polysiloxane;
The 3rd step: add remaining polyisocyanates after reacting completely, be warming up to 80 ℃ of reactions and obtain performed polymer;
The 4th step: chainextender is mixed with water, performed polymer is slowly added in the water that contains chainextender of gained, then add triethylamine neutralization, obtain aqueous polyurethane.
The product of embodiment 5-12 is carried out to performance test as follows:
1, the mensuration of solids content
Press the mensuration of GB1725-79, quality W weighs to obtain after the culture dish of dried and clean is dried completely, by decrement method, take the culture dish that 1.5-2g polyaminoester emulsion is placed in oven dry, make sample be uniformly distributed in the bottom of container, the W1 that weighs to obtain, then puts it into 120 ℃ of oven dry in baking oven, takes out to be cooled to room temperature and to weigh, put into oven drying again and be no more than 0.01g until weigh difference for twice, be designated as W2.The solid content of emulsion is by (W2-W)/(W1-W) calculate.
2, stability test
At room temperature standing, observe and whether have demixing phenomenon to occur.Take the index that the stratification time is Stability Determination.The emulsion stratification time of poor stability is several days even several hours; The good emulsion stratification time of stability is the 2-3 month; The emulsion stratification time of good stability can reach more than 3 months.
3, surface tension test
Use the full-automatic interfacial tensimeter of A101 type of U.S. Ke Luo Industrial Co., Ltd to measure surface tension and micelle-forming concentration (CMC).Prepare the aqueous polyurethane of a series of different concns, the surface tension of sample solution while adopting adopting platinum plate method to measure 25 ℃, each sample replication three times, then averages.
4, water resistance test:
Sample coating, on the test plate (panel) of tetrafluoroethylene, is at room temperature placed to 7d seasoning film forming.To film (the about 0.14mm of thickness) be cut into 30mm * 30mm size; At 25 ℃, immerse in tap water, after 24h, observe or weigh its quality change before and after immersing.The quality that weighs sample before and after immersing, is respectively W
1, W
2, water-intake rate=(W
1-W
2)/W
1* 100%.Observe the outward appearance after water-fast 24 hours simultaneously.
5, timber cracking resistance experiment
By three kinds of seeds, each 15 of Cortex Fraxini mandshuricae, toothed oak wood, birch lumbers, be made into same length, same size.All sheet material is together stacked, between various sheet material, staggered mutually.Before experiment, the equal leakless of each sheet material, meanwhile, one end is coated with the aqueous polyurethane sealing oil that the present invention obtains, and the other end is not coated with.All sheet material is placed on to the indoor natural seasoning that carries out.Experiment showed, that scribbling aqueous polyurethane seals oily sheet material, in 3 months, do not ftracture, there is good anti-cracking performance.
6, automatically cleaning test
Sample coating, on the test plate (panel) of tetrafluoroethylene, is at room temperature placed to 7d seasoning film forming.To film (the about 0.14mm of thickness) be cut into 30mm * 30mm size, prepare 3 samples.At 25 ℃, immerse in glycerine solution, with the speed of 60cm/min, lift, at 70 ℃ after dry 15min by the deionized water drop of 4 μ L in coatingsurface, get the testing mean of three samples.Experimental results show that contact angle is 158-162 degree, aqueous polyurethane of the present invention has good self-cleaning function.
7, from fire retardancy test
Sample coating, on the test plate (panel) of tetrafluoroethylene, is at room temperature placed to 7d seasoning film forming, and will film (the about 0.14mm of thickness) is cut into long 125mm, and the size of wide 13.0mm is prepared 3 samples.Combustionproperty is carried out according to UL94 standard, measures 3 samples.Experiment showed, that the combustionproperty of each sample is all in V-0 rank, aqueous polyurethane of the present invention has good in flame retardant properties.
8, highly air-permeable can be tested
Sample coating, on the test plate (panel) of tetrafluoroethylene, is at room temperature placed to 7d seasoning film forming, and will film (the about 0.14mm of thickness) is cut into 30mm * 30mm size.Permeating degree tester device is placed on the level attitude that there is no vibration, film is clipped on testing tool, in 30s, pressure reduction is adjusted to 1.00 ± 0.01kPa, then get started and measure the airshed that sees through sample, each sample replication three times, averages.Evidence, aqueous polyurethane ventilation property of the present invention reaches 170cm
3/ cm
2/ second, aqueous polyurethane of the present invention has highly air-permeable energy.
By above-mentioned data, can know, the aqueous polyurethane that the present invention obtains has good water tolerance and stability, illustrates that internal emulsifying agent and siloxane chain have played corresponding effect.
Claims (10)
1. an aqueous polyurethane, is characterized in that, by the raw material that comprises polyether glycol, polyisocyanates, internal emulsifying agent, polyamino siloxanes, chainextender and water is synthetic, obtains.
2. aqueous polyurethane as claimed in claim 1, is characterized in that, described polyamino siloxanes is one or more in diamino siloxanes, diamino polysiloxane, triamino siloxanes and triamino siloxanes.
3. aqueous polyurethane as claimed in claim 1, is characterized in that, described polyisocyanates is TDI, MD1 or PAPI.
4. aqueous polyurethane as claimed in claim 1, is characterized in that, described polyether glycol is one or more in polyoxypropyleneglycol, polyoxytrimethylene triol and polytetrahydrofuran diol.
5. aqueous polyurethane as claimed in claim 1, is characterized in that, described internal emulsifying agent is 2,2-dimethylolpropionic acid, 2,2-dimethylol propionic acid, 2,2-dihydroxy ethyl butyric acid, 2,2-dihydroxy ethyl propionic acid, 2,3-dimethylolpropionic acid, 2,3-dimethylol propionic acid, 2, one or more in 3-dihydroxy ethyl butyric acid and 2,3-dihydroxy ethyl propionic acid.
6. aqueous polyurethane as claimed in claim 1, is characterized in that, described chainextender is polyhydroxy phosphate.
7. aqueous polyurethane as claimed in claim 6, is characterized in that, described polyhydroxy phosphate has following structure:
In above formula, R
1, R
2, R
3in at least contain an oh group, R
1, R
2, R
3independently represent alcohol straight or branched, that saturated or undersaturated alcohol, alkyl, epoxy compounds or open loop of epoxy compound form.
8. aqueous polyurethane as claimed in claim 7, is characterized in that, described polyhydroxy phosphate is dihydroxyl phosphoric acid ester, tetrahydroxy phosphoric acid ester or hexahydroxy-phosphoric acid ester, R
1, R
2and R
3in at least one contains dihydroxyl structure.
9. the preparation method of the aqueous polyurethane described in any one in claim 1-8, is characterized in that, concrete steps comprise:
The first step: polyether glycol 100 weight parts, polyisocyanates 120-140 weight part and internal emulsifying agent 3-5 weight part are uniformly mixed under 7-10 degree Celsius, under agitation add polyamino siloxanes 2-6 weight part to react, form side chain containing the compound of polysiloxane; Or, polyether glycol 100 weight parts and polyisocyanates 120-140 weight part are uniformly mixed under 7-10 degree Celsius, under agitation add polyamino siloxanes 2-6 weight part to react, form side chain containing the compound of polysiloxane, then add internal emulsifying agent 3-5 weight part;
Second step: add polyisocyanates 10-50 weight part after reacting completely, be warming up to 50-80 ℃ of reaction and obtain performed polymer;
The 3rd step: chainextender 14-16 weight part is mixed with water 350-450 weight part, performed polymer is slowly added in the water that contains chainextender of gained, then add triethylamine neutralization, obtain aqueous polyurethane.
10. the preparation method of aqueous polyurethane as claimed in claim 9, is characterized in that, the reaction times of the described the first step is 0.5-3 hour, and the reaction times of described second step is 2-6 hour.
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| CN105037680A (en) * | 2015-06-23 | 2015-11-11 | 上海东和胶粘剂有限公司 | Permeable modified waterborne polyurethane waterproof agent |
| CN105753379A (en) * | 2014-12-17 | 2016-07-13 | 广州市领科化工有限公司 | Four-component aqueous polyurethane mortar floor material |
| CN107502268A (en) * | 2017-08-18 | 2017-12-22 | 佛山市永恒达新材料科技有限公司 | A kind of preparation method for plastic bonding adhesive |
| CN107502269A (en) * | 2017-08-18 | 2017-12-22 | 佛山市永恒达新材料科技有限公司 | Adhesive for plastic bonding |
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| CN105753379A (en) * | 2014-12-17 | 2016-07-13 | 广州市领科化工有限公司 | Four-component aqueous polyurethane mortar floor material |
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| CN108687903A (en) * | 2018-04-24 | 2018-10-23 | 广州精点高分子材料制品有限公司 | A kind of application method based on closed NCO group ceramics wood |
| CN108818816A (en) * | 2018-04-24 | 2018-11-16 | 广州精点高分子材料制品有限公司 | A kind of ceramics wood and manufacturing method based on closed NCO |
| CN108818817A (en) * | 2018-04-24 | 2018-11-16 | 广州精点高分子材料制品有限公司 | A kind of ceramic wooden and manufacturing method of high molecular polymer filled-type |
| CN108864399A (en) * | 2018-07-06 | 2018-11-23 | 汕头大学 | A kind of organic-silicon-modified flame retardant polyurethane and its preparation |
| CN108864399B (en) * | 2018-07-06 | 2020-12-29 | 汕头大学 | Organic silicon modified flame-retardant polyurethane and preparation thereof |
| CN109401282A (en) * | 2018-09-11 | 2019-03-01 | 苏州市雄林新材料科技有限公司 | A kind of dress ornament highly-flexible TPU film and preparation method thereof |
| CN113637404A (en) * | 2021-08-17 | 2021-11-12 | 孙建忠 | Anti-penetration curing waterproof agent for building wall and preparation method thereof |
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