CN106589307A - Waterborne polyurethane coating agent with good water resistance and flame retardance and preparation method thereof - Google Patents
Waterborne polyurethane coating agent with good water resistance and flame retardance and preparation method thereof Download PDFInfo
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- CN106589307A CN106589307A CN201611205619.1A CN201611205619A CN106589307A CN 106589307 A CN106589307 A CN 106589307A CN 201611205619 A CN201611205619 A CN 201611205619A CN 106589307 A CN106589307 A CN 106589307A
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 239000011527 polyurethane coating Substances 0.000 title claims abstract description 14
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 39
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 35
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000003063 flame retardant Substances 0.000 claims abstract description 28
- 239000004814 polyurethane Substances 0.000 claims abstract description 21
- 229920002635 polyurethane Polymers 0.000 claims abstract description 21
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims abstract description 18
- 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 claims abstract description 16
- 235000019441 ethanol Nutrition 0.000 claims abstract description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 14
- -1 perfluoro-alkyl ethyl alcohol Chemical compound 0.000 claims abstract description 12
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 7
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims abstract description 7
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229920000570 polyether Polymers 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 16
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 11
- 239000000839 emulsion Substances 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000012948 isocyanate Substances 0.000 claims description 8
- VLCAYQIMSMPEBW-UHFFFAOYSA-N methyl 3-hydroxy-2-methylidenebutanoate Chemical compound COC(=O)C(=C)C(C)O VLCAYQIMSMPEBW-UHFFFAOYSA-N 0.000 claims description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 6
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 6
- 150000002334 glycols Chemical class 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 6
- 229940059574 pentaerithrityl Drugs 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 239000011574 phosphorus Substances 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- KKUKTXOBAWVSHC-UHFFFAOYSA-N Dimethylphosphate Chemical compound COP(O)(=O)OC KKUKTXOBAWVSHC-UHFFFAOYSA-N 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000012467 final product Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 3
- 235000019260 propionic acid Nutrition 0.000 claims description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- DGADNPLBVRLJGD-UHFFFAOYSA-N 2,3-dihydroxy-2-methylpropanoic acid Chemical compound OCC(O)(C)C(O)=O DGADNPLBVRLJGD-UHFFFAOYSA-N 0.000 claims 1
- 239000011248 coating agent Substances 0.000 abstract description 6
- 229910052731 fluorine Inorganic materials 0.000 abstract description 4
- 239000011737 fluorine Substances 0.000 abstract description 4
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 abstract description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 abstract 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 abstract 1
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 abstract 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 abstract 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 abstract 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 abstract 1
- 231100000053 low toxicity Toxicity 0.000 abstract 1
- 229920002521 macromolecule Polymers 0.000 abstract 1
- 239000004753 textile Substances 0.000 abstract 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 abstract 1
- 239000004744 fabric Substances 0.000 description 6
- 150000002513 isocyanates Chemical class 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- 238000006757 chemical reactions by type Methods 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000002574 poison Substances 0.000 description 2
- 239000005871 repellent Substances 0.000 description 2
- 230000002940 repellent Effects 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- DBXBTMSZEOQQDU-UHFFFAOYSA-N 3-hydroxyisobutyric acid Chemical compound OCC(C)C(O)=O DBXBTMSZEOQQDU-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229920004933 Terylene® Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000004079 fireproofing Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000004812 organic fluorine compounds Chemical class 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005406 washing Methods 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic 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
- 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
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/288—Compounds containing at least one heteroatom other than oxygen or nitrogen
- C08G18/2885—Compounds containing at least one heteroatom other than oxygen or nitrogen containing halogen atoms
-
- 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
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- 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
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
-
- 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
- C08G18/3878—Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus
- C08G18/3882—Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus having phosphorus bound to oxygen only
-
- 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
- C08G18/4825—Polyethers containing two hydroxy 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
- C08G18/65—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
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
-
- 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
-
- 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
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
Landscapes
- 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)
- Compositions Of Macromolecular Compounds (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention discloses a waterborne polyurethane coating agent with good water resistance and flame retardance, consisting of the following raw materials in parts by weight: 40-60 parts of toluene diisocyanate, 13-30 parts of polyether glycol, 6-12 parts of phosphorus oxychloride, 4-10 parts of hydroxyethyl methacrylate, 20-40 parts of anhydrous diethyl ether, 20-35 parts of triethylamine, 4-14 parts of diethanolamine, an appropriate amount of methanol, 3-7 parts of 1,4-dibutyl alcohol, 2-6 parts of dimethylolpropionic acid, 4-12 parts of perfluoro-alkyl ethyl alcohol, an appropriate amount of acetone, an appropriate amount of ethanol, and 2-5 parts of pentaerythritol. According to the preparation method disclosed by the invention, a phosphonate flame-retardant intermediate is introduced into a macromolecular chain of polyurethane to form halogen-free low-toxicity flame-retardant macromolecules, sponges, textiles and the like to which the coating agent is applied have relatively high flame retardance, and meanwhile, fluorine is introduced into waterborne polyurethane molecules to improved the water resistance of the waterborne polyurethane coating agent.
Description
Technical field
The present invention relates to aqueous polyurethane flame retardant coating agent and preparation method thereof, more particularly to a kind of water proof fire retardant performance is excellent
Good Aqueous Polyurethane Coating Agent and preparation method thereof.
Technical background
Sponge runs into naked light and easily burns, such as in sponge surface after special polyurethane material is processed, sponge table
Face can be good flame retardant effect.It is conventionally used to mechanical shockproof, the sponge surface coating treatment of heat-insulating flame-retardant is that oiliness is gathered mostly
Urethane, it is well known that the VOC in oiliness Polyurethane impairs human body health, with the enhancing of mankind's environmental consciousness, seeks
The sponge surface coating of environmental protection is imperative.
Antiflaming finishing agent, also known as fire retardant, incombustible agent, fire-proofing chemical or fireproof agent, is that one kind can give fabric, sponge etc.
The functional aid of combustibles flame retardancy；It is divided into additive flame retardant and reactive flame retardant according to its application mode.With respect to filler
For flame-retarded technology, reaction-type flame-retarding technology can more reach the hypotoxic target of the low smoke of efficient high fire-retardance.Reaction-type flame-retarding skill
Art is by by ignition-proof element（Halogen, phosphorus, antimony, silicon, nitrogen）It is introduced in combustibles face coat so as to reach fire-retardant purpose.
Yu Danqi, Chen Guoqiang et al. are at which《The synthesis of new phosphorus flame retardant and the microwave grafting to real silk》In one text,
The phosphoric acrylic ester with double bond is synthesized in two steps using phosphorus oxychloride and hydroxyethyl methylacrylate, absolute methanol has
Machine phosphorus flame retardant, carries out graft copolymerization process using the method for microwave exposure afterwards to real silk, obtains preferable fire resistance,
And after washing 30 times, fabric still has preferable anti-flammability, illustrates that the durability of this kind of flame-proof treatment is preferable.
The present invention introduces terminal hydroxy group on phosphoric acrylic ester chain, and part replaces polyhydric alcohol to react with isocyanates, poly-
Phosphonate Flame Retardant intermediate is introduced in the macromolecular chain of urethane, Halogen, low-poison and combustion-resisting macromole is defined, after applying coating agent
Sponge, fabric etc. are with higher fire resistance, while fluorine element is introduced in aqueous polyurethane molecule, reduce aqueous polyurethane
Surface energy, improve Aqueous Polyurethane Coating Agent resistance to water.
The content of the invention
For the deficiencies in the prior art, the present invention provide a kind of Aqueous Polyurethane Coating Agent of water proof fire retardant function admirable and
Its preparation method.
A kind of Aqueous Polyurethane Coating Agent of water proof fire retardant function admirable, is made up of the raw material of following weight portion：Toluene two
Isocyanates 40-60 parts, polyether Glycols 13-30 parts, phosphorus oxychloride 6-12 part, hydroxyethyl methylacrylate 4-10 parts are anhydrous
Ether 20-40 parts, triethylamine 20-35 parts, diethanolamine 4-14 parts, appropriate methanol ,-two butanol 3-7 parts of Isosorbide-5-Nitrae, dihydroxymethyl third
Sour 2-6 parts, perfluoroalkyl ethyl alcohol 4-12 parts, acetone in proper, appropriate amount of ethanol, tetramethylolmethane 2-5 parts.
Comprise the following steps that：
（1）The preparation of terminal hydroxy group phosphonium flame retardant：
1., there-necked flask is placed in low-temp reaction bath, phosphorus oxychloride and absolute ether is added, when temperature is down to 0-5 DEG C, is started
The mixed liquor of Deca hydroxyethyl methylacrylate and 1/7 part of triethylamine, stirs in Deca, continues stirring 1- after completion of dropping
2 hours, Deca methanol and 1/7 portion of triethylamine mixed liquor, continued stirring reaction 5-7 hour, are stood overnight afterwards, and sucking filtration is straight
To the clear solution for obtaining clarifying, methylacryoyloxyethyl Dimethyl phosphate is concentrated to give；
2. above-mentioned product and diethanolamine, methanol are added in there-necked flask, leads to nitrogen protection, at ambient temperature stirring at low speed 50-
70 minutes, 40-50 DEG C of reaction 4-5 hour is warming up to afterwards, distillation removes solvent, obtains terminal hydroxy group phosphor-containing flame-proof monomer；
（2）The preparation of the end-NCO base polyurethane prepolymer for use as of phosphor-containing flame-proof type：
Toluene di-isocyanate(TDI), polyether Glycols are added in the four-hole boiling flask equipped with agitator, condensing reflux pipe and thermometer
And step（1）Terminal hydroxy group phosphor-containing flame-proof monomer, at 70-80 DEG C react 1-3 hours, at being cooled to 65-70 DEG C progressively with Isosorbide-5-Nitrae-
Two butanol, dihydromethyl propionic acid reaction 2-4 hours, are obtained the end-NCO based polyurethanes performed polymers of phosphor-containing flame-proof type；
（3）The Organic fluoride of phosphor-containing flame-proof type blocks the preparation of aqueous polyurethane emulsion：
Perfluoroalkyl ethyl alcohol is added in above-mentioned base polyurethane prepolymer for use as reactant liquor, 25-40 is reacted at 65-80 DEG C of bath temperature
Minute, acetone regulation system viscosity is added, and is cooled to room temperature, with stirring 15-25 minutes in the remaining triethylamine of addition, contained
The Organic fluoride end-blocking aqueous polyurethane emulsion of phosphorus flame retardant type；
（4）Under room temperature, to step（3）Ethanol, tetramethylolmethane mixing are added in emulsion, 40-60 DEG C is warming up to, in 7000-
0.5-1.5 hours are stirred under 8000rpm Strong shears, a kind of Aqueous Polyurethane Coating Agent of water proof fire retardant function admirable is obtained final product.
Compared with prior art, the present invention has advantages below：
（1）The present invention is synthesized with double bond phosphorous third using phosphorus oxychloride and hydroxyethyl methylacrylate, absolute methanol
Olefin(e) acid ester, on phosphoric acrylic ester chain introduces terminal hydroxy group with diethanolamine reaction using double bond afterwards, and part replaces polyhydric alcohol
React with isocyanates, Phosphonate Flame Retardant intermediate is introduced in the macromolecular chain of polyurethane, Halogen, low-poison and combustion-resisting is defined big
, with higher fire resistance, under high temperature, halogen-free release, nontoxic for molecule, sponge, fabric after applying coating agent etc., low cigarette.
（2）While-the CF in organofluorine compound3Surface energy it is low, make the intermolecular work of polymer thing containing C-F keys
It is firmly weaker, thus fluorine-containing polymer has relatively low surface free energy, with preferable water repellent, oil repellent, therefore will be complete
Fluoroalkyl ethyl alcohol is blocked to aqueous polyurethane molecule, and fluorine-containing carbochain is in the two ends of aqueous polyurethane molecule, can be with
The surface energy of aqueous polyurethane is reduced, water-fast, the pollution resistance of aqueous polyurethane glued membrane is improved.
Specific embodiment
A kind of Aqueous Polyurethane Coating Agent of water proof fire retardant function admirable, is made up of the raw material of following weight portion：Toluene two
Isocyanates 55, polyether Glycols 27, phosphorus oxychloride 9, hydroxyethyl methylacrylate 7, absolute ether 34, triethylamine 30, diethyl
Hydramine 10, appropriate methanol ,-two butanol 6 of Isosorbide-5-Nitrae, dihydromethyl propionic acid 4, perfluoroalkyl ethyl alcohol 10, acetone in proper, appropriate amount of ethanol,
Tetramethylolmethane 4.
Comprise the following steps that：
（1）The preparation of terminal hydroxy group phosphonium flame retardant：
1., there-necked flask is placed in low-temp reaction bath, phosphorus oxychloride and absolute ether is added, when temperature is down to 0 DEG C, starts drop
The mixed liquor of methylate 2-(Acryloyloxy)ethanol and 1/7 part of triethylamine, stirs in Deca, continues stirring 1 little after completion of dropping
When, Deca methanol and 1/7 portion of triethylamine mixed liquor, continue stirring reaction 6 hours afterwards, are stood overnight, and sucking filtration is until obtain
To the clear solution of clarification, methylacryoyloxyethyl Dimethyl phosphate is concentrated to give；
2. above-mentioned product and diethanolamine, methanol are added in there-necked flask, leads to nitrogen protection, at ambient temperature stirring at low speed 60
Minute, 45 DEG C are warming up to afterwards reacts 5 hours, distillation removes solvent, obtains terminal hydroxy group phosphor-containing flame-proof monomer；
（2）The preparation of the end-NCO base polyurethane prepolymer for use as of phosphor-containing flame-proof type：
Toluene di-isocyanate(TDI), polyether Glycols are added in the four-hole boiling flask equipped with agitator, condensing reflux pipe and thermometer
And step（1）Terminal hydroxy group phosphor-containing flame-proof monomer, at 75 DEG C react 2 hours, be cooled at 67 DEG C progressively with-two butanol of Isosorbide-5-Nitrae, two
Hydroxymethyl propionic acid reacts 3 hours, and the end-NCO based polyurethanes performed polymers of phosphor-containing flame-proof type are obtained；
（3）The Organic fluoride of phosphor-containing flame-proof type blocks the preparation of aqueous polyurethane emulsion：
Perfluoroalkyl ethyl alcohol is added in above-mentioned base polyurethane prepolymer for use as reactant liquor, is reacted 30 minutes at 75 DEG C of bath temperature,
Acetone regulation system viscosity is added, and is cooled to room temperature, with stirring 20 minutes in the remaining triethylamine of addition, obtain phosphor-containing flame-proof type
Organic fluoride end-blocking aqueous polyurethane emulsion；
（4）Under room temperature, to step（3）Ethanol, tetramethylolmethane mixing are added in emulsion, 50 DEG C is warming up to, in 8000rpm Strong shears
Lower stirring 1 hour, obtains final product a kind of Aqueous Polyurethane Coating Agent of water proof fire retardant function admirable.
Fire resistance is tested：With terylene Oxford tent cloth as process and test fabric, vertically fired using GB/T5455-1997
The experiment detection of burning method, must fire time 0s, smoldering time 0s；The long 10.6cm of damage charcoal.
Claims (2)
1. a kind of Aqueous Polyurethane Coating Agent of water proof fire retardant function admirable, it is characterised in that by the raw material group of following weight portion
Into：Toluene di-isocyanate(TDI) 40-60, polyether Glycols 13-30 parts, phosphorus oxychloride 6-12 part, hydroxyethyl methylacrylate 4-10
Part, absolute ether 20-40 parts, triethylamine 20-35 parts, diethanolamine 4-14 parts, appropriate methanol ,-two butanol 3-7 parts of Isosorbide-5-Nitrae, dihydroxy
Methylpropanoic acid 2-6 parts, perfluoroalkyl ethyl alcohol 4-12 parts, acetone in proper, appropriate amount of ethanol, tetramethylolmethane 2-5 parts.
2. the preparation method of the Aqueous Polyurethane Coating Agent of a kind of water proof fire retardant function admirable according to claims 1,
Characterized in that, comprising the following steps that：
（1）The preparation of terminal hydroxy group phosphonium flame retardant：
1., there-necked flask is placed in low-temp reaction bath, phosphorus oxychloride and absolute ether is added, when temperature is down to 0-5 DEG C, is started
The mixed liquor of Deca hydroxyethyl methylacrylate and 1/7 part of triethylamine, stirs in Deca, continues stirring 1- after completion of dropping
2 hours, Deca methanol and 1/7 portion of triethylamine mixed liquor, continued stirring reaction 5-7 hour, are stood overnight afterwards, and sucking filtration is straight
To the clear solution for obtaining clarifying, methylacryoyloxyethyl Dimethyl phosphate is concentrated to give；
2. above-mentioned product and diethanolamine, methanol are added in there-necked flask, leads to nitrogen protection, at ambient temperature stirring at low speed 50-
70 minutes, 40-50 DEG C of reaction 4-5 hour is warming up to afterwards, distillation removes solvent, obtains terminal hydroxy group phosphor-containing flame-proof monomer；
（2）The preparation of the end-NCO base polyurethane prepolymer for use as of phosphor-containing flame-proof type：
Toluene di-isocyanate(TDI), polyether Glycols are added in the four-hole boiling flask equipped with agitator, condensing reflux pipe and thermometer
And step（1）Terminal hydroxy group phosphor-containing flame-proof monomer, at 70-80 DEG C react 1-3 hours, at being cooled to 65-70 DEG C progressively with Isosorbide-5-Nitrae-
Two butanol, dihydromethyl propionic acid reaction 2-4 hours, are obtained the end-NCO based polyurethanes performed polymers of phosphor-containing flame-proof type；
（3）The Organic fluoride of phosphor-containing flame-proof type blocks the preparation of aqueous polyurethane emulsion：
Perfluoroalkyl ethyl alcohol is added in above-mentioned base polyurethane prepolymer for use as reactant liquor, 25-40 is reacted at 65-80 DEG C of bath temperature
Minute, acetone regulation system viscosity is added, and is cooled to room temperature, with stirring 15-25 minutes in the remaining triethylamine of addition, contained
The Organic fluoride end-blocking aqueous polyurethane emulsion of phosphorus flame retardant type；
（4）Under room temperature, to step（3）Ethanol, tetramethylolmethane mixing are added in emulsion, 40-60 DEG C is warming up to, in 7000-
0.5-1.5 hours are stirred under 8000rpm Strong shears, a kind of Aqueous Polyurethane Coating Agent of water proof fire retardant function admirable is obtained final product.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109438643A (en) * | 2018-11-08 | 2019-03-08 | 合众（佛山）化工有限公司 | A kind of biology base fluorine modified aqueous polyurethane resin and preparation method thereof |
| CN109652984A (en) * | 2018-12-12 | 2019-04-19 | 上海雅运新材料有限公司 | A kind of fabrics flame resistance coating finishing agent composition and preparation method thereof |
| CN109880055A (en) * | 2019-02-27 | 2019-06-14 | 黑龙江省科学院石油化学研究院 | A kind of perfluoroalkyl chain end-capped comb-structure urethane acrylate and preparation method thereof |
| CN110734658A (en) * | 2019-10-18 | 2020-01-31 | 湖南罗比特化学材料有限公司 | fireproof flame-retardant waterborne polyurethane UV coating and preparation method thereof |
| CN110885549A (en) * | 2019-11-13 | 2020-03-17 | 惠州市高峰创兴实业有限公司 | Formula and preparation process of waterproof flame-retardant sponge |
| CN111188202A (en) * | 2020-02-10 | 2020-05-22 | 广州市新荔缘鞋业有限公司 | Flame-retardant high-temperature-resistant composite fabric and preparation method thereof |
| CN113354790A (en) * | 2021-06-25 | 2021-09-07 | 上海伟星新材料科技有限公司 | Fluorine-containing and phosphorus-containing waterborne polyurethane material and preparation method thereof |
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| CN109438643A (en) * | 2018-11-08 | 2019-03-08 | 合众（佛山）化工有限公司 | A kind of biology base fluorine modified aqueous polyurethane resin and preparation method thereof |
| CN109652984A (en) * | 2018-12-12 | 2019-04-19 | 上海雅运新材料有限公司 | A kind of fabrics flame resistance coating finishing agent composition and preparation method thereof |
| CN109652984B (en) * | 2018-12-12 | 2021-07-20 | 太仓宝霓实业有限公司 | A kind of fabric flame retardant coating finishing agent composition and preparation method thereof |
| CN109880055A (en) * | 2019-02-27 | 2019-06-14 | 黑龙江省科学院石油化学研究院 | A kind of perfluoroalkyl chain end-capped comb-structure urethane acrylate and preparation method thereof |
| CN109880055B (en) * | 2019-02-27 | 2022-01-28 | 黑龙江省科学院石油化学研究院 | Preparation method of perfluoroalkyl chain terminated polyurethane acrylate with comb-shaped structure |
| CN110734658A (en) * | 2019-10-18 | 2020-01-31 | 湖南罗比特化学材料有限公司 | fireproof flame-retardant waterborne polyurethane UV coating and preparation method thereof |
| CN110734658B (en) * | 2019-10-18 | 2021-10-15 | 湖南罗比特化学材料有限公司 | A fire-retardant and flame-retardant water-based UV coating and preparation method thereof |
| CN110885549A (en) * | 2019-11-13 | 2020-03-17 | 惠州市高峰创兴实业有限公司 | Formula and preparation process of waterproof flame-retardant sponge |
| CN111188202A (en) * | 2020-02-10 | 2020-05-22 | 广州市新荔缘鞋业有限公司 | Flame-retardant high-temperature-resistant composite fabric and preparation method thereof |
| CN111188202B (en) * | 2020-02-10 | 2022-07-12 | 山东大统服饰有限责任公司 | Flame-retardant high-temperature-resistant composite fabric and preparation method thereof |
| CN113354790A (en) * | 2021-06-25 | 2021-09-07 | 上海伟星新材料科技有限公司 | Fluorine-containing and phosphorus-containing waterborne polyurethane material and preparation method thereof |
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Application publication date: 20170426 |