CN112480348A - Phosphorus-boron hybrid chain prepolymer block polyurethane leather flame-retardant water-based coating agent and preparation method and application thereof - Google Patents
Phosphorus-boron hybrid chain prepolymer block polyurethane leather flame-retardant water-based coating agent and preparation method and application thereof Download PDFInfo
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- CN112480348A CN112480348A CN202011311404.4A CN202011311404A CN112480348A CN 112480348 A CN112480348 A CN 112480348A CN 202011311404 A CN202011311404 A CN 202011311404A CN 112480348 A CN112480348 A CN 112480348A
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- water
- finishing agent
- chain prepolymer
- leather
- block polyurethane
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 239000010985 leather Substances 0.000 title claims abstract description 45
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 44
- 239000004814 polyurethane Substances 0.000 title claims abstract description 44
- 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 title claims abstract description 42
- 239000003063 flame retardant Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000011248 coating agent Substances 0.000 title claims description 20
- GDFCWFBWQUEQIJ-UHFFFAOYSA-N [B].[P] Chemical compound [B].[P] GDFCWFBWQUEQIJ-UHFFFAOYSA-N 0.000 title description 35
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 43
- 229920001577 copolymer Polymers 0.000 claims abstract description 25
- 239000002131 composite material Substances 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 20
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims abstract description 7
- 239000001768 carboxy methyl cellulose Substances 0.000 claims abstract description 7
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims abstract description 7
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims abstract description 7
- 239000003086 colorant Substances 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 4
- DEFTVJAJYJMJNL-UHFFFAOYSA-N P(=O)(=O)B Chemical group P(=O)(=O)B DEFTVJAJYJMJNL-UHFFFAOYSA-N 0.000 claims abstract 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 15
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 14
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 238000000227 grinding Methods 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 239000008096 xylene Substances 0.000 claims description 11
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 9
- DQYBDCGIPTYXML-UHFFFAOYSA-N ethoxyethane;hydrate Chemical compound O.CCOCC DQYBDCGIPTYXML-UHFFFAOYSA-N 0.000 claims description 9
- GDXHBFHOEYVPED-UHFFFAOYSA-N 1-(2-butoxyethoxy)butane Chemical compound CCCCOCCOCCCC GDXHBFHOEYVPED-UHFFFAOYSA-N 0.000 claims description 8
- 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 8
- 229910052796 boron Inorganic materials 0.000 claims description 8
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 8
- 239000003085 diluting agent Substances 0.000 claims description 8
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 6
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 5
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 5
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 4
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 4
- 239000002518 antifoaming agent Substances 0.000 claims description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- 238000009826 distribution Methods 0.000 claims description 3
- 230000003472 neutralizing effect Effects 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 239000012860 organic pigment Substances 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920002545 silicone oil Polymers 0.000 claims description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 2
- 238000013329 compounding Methods 0.000 claims 2
- 239000013530 defoamer Substances 0.000 claims 2
- 239000002671 adjuvant Substances 0.000 claims 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 claims 1
- 239000000835 fiber Substances 0.000 claims 1
- 229910052736 halogen Inorganic materials 0.000 abstract description 8
- 150000002367 halogens Chemical class 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 7
- 239000000779 smoke Substances 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000013461 design Methods 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 231100000053 low toxicity Toxicity 0.000 abstract description 3
- 238000007761 roller coating Methods 0.000 abstract description 3
- 238000005507 spraying Methods 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- LFPIHDQZHBXSGD-UHFFFAOYSA-N P(=O)(=O)[B] Chemical compound P(=O)(=O)[B] LFPIHDQZHBXSGD-UHFFFAOYSA-N 0.000 abstract 1
- 238000007334 copolymerization reaction Methods 0.000 abstract 1
- 230000007774 longterm Effects 0.000 abstract 1
- 238000000034 method Methods 0.000 description 9
- 239000004576 sand Substances 0.000 description 9
- 239000012752 auxiliary agent Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 239000002649 leather substitute Substances 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000000498 cooling water Substances 0.000 description 3
- 238000005034 decoration Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000010907 mechanical stirring Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 239000012796 inorganic flame retardant Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000002464 physical blending Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 230000002110 toxicologic effect Effects 0.000 description 1
- 231100000027 toxicology Toxicity 0.000 description 1
- 238000002834 transmittance 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
- C08G18/28—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
- C08G18/6541—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/34
-
- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
- C08G18/6461—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63 having phosphorus
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
-
- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C11/00—Surface finishing of leather
-
- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C11/00—Surface finishing of leather
- C14C11/003—Surface finishing of leather using macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C11/00—Surface finishing of leather
- C14C11/003—Surface finishing of leather using macromolecular compounds
- C14C11/006—Surface finishing of leather using macromolecular compounds using polymeric products of isocyanates (or isothiocyanates) with compounds having active hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
Abstract
本发明涉及皮革涂饰剂技术领域，具体涉及磷硼杂链预聚物嵌段聚氨酯皮革阻燃水性涂饰剂及其制备方法与应用。所述涂饰剂的原料组成包括：11.5～13.5％着色剂、2.5～3.5％羧甲基纤维素、3.0～4.0％复合助剂、80.0～82.0％磷硼杂链预聚物嵌段聚氨酯水性共聚物，该共聚物的结构式如下：本发明通过分子设计与合成，本发明将磷硼阻燃元素和亲水基团以化学键形式键接于聚氨酯分子结构之中，得到磷硼杂链预聚物嵌段聚氨酯水性共聚物，并以这种共聚物为基料制备适用于皮革表面辊涂或喷涂的涂饰剂，经该涂饰剂处理的皮革具有低毒环保、低烟无卤、长效阻燃、防水耐磨和装饰性强、手感舒适等协效复合功能。The invention relates to the technical field of leather finishing agents, in particular to a fire-retardant aqueous finishing agent for phosphoborane chain prepolymer block polyurethane leather and a preparation method and application thereof. The raw material composition of the finishing agent includes: 11.5-13.5% colorant, 2.5-3.5% carboxymethyl cellulose, 3.0-4.0% compound auxiliary, 80.0-82.0% phosphoborane chain prepolymer block polyurethane water-based copolymerization The structural formula of the copolymer is as follows: 
Through molecular design and synthesis, the present invention bonds phosphoboron flame retardant elements and hydrophilic groups in the molecular structure of polyurethane in the form of chemical bonds to obtain a phosphoborane chain prepolymer block polyurethane water-based copolymer, and uses This copolymer is used as the base material to prepare a finishing agent suitable for roller coating or spraying on the leather surface. The leather treated with the finishing agent has the advantages of low toxicity, environmental protection, low smoke and halogen free, long-term flame retardant, waterproof and wear-resistant, and strong decorative properties. Comfortable hand feeling and other synergistic composite functions.
Description
Technical Field
The invention relates to the technical field of leather finishing agents, in particular to a phosphorus-boron heterochain prepolymer segmented polyurethane leather flame-retardant water-based finishing agent and a preparation method and application thereof.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
The leather finishing agent is a general name of leather auxiliary agents for leather surface finishing protection and leather beautification, and is prepared by a film forming substance, a coloring material, a solvent and the auxiliary agents according to a certain proportion, wherein the film forming substance is the basis of the leather finishing agent. Leather belongs to flammable materials, is easy to burn when meeting open fire, has fire hazard in the using process, and has high attention paid to flame-retardant fire prevention of leather by technical workers and engineering technicians at home and abroad. Researches show that elements such as halogen, phosphorus, boron, nitrogen, silicon and the like have excellent flame retardant effect in the combustion process of organic materials, the halogen-containing flame retardant is limited due to the generation of highly toxic gas in the combustion process, and the element flame retardant such as P, B, N, Si has the flame retardant functions of no halogen, low smoke, environmental protection and high efficiency. P, B, N, Si and other elements are synthesized into the polymer with intrinsic flame retardant function through molecular design and synthesis, which is an effective way for preparing halogen-free low-smoke long-acting flame retardant polymer materials.
Document 1 discloses a waterborne polyurethane-acrylate hybrid resin, a preparation method thereof and application thereof in a leather finishing agent, wherein the prepared waterborne polyurethane-acrylate hybrid resin is simple and controllable in preparation process, and the leather finishing agent prepared from the waterborne polyurethane-acrylate hybrid resin is suitable for the field of high-end leather finishing agents and has the advantages of high weather resistance, smooth hand feeling, good anti-sticking performance, good anti-whitening performance, good filler coating performance, high black transmittance and good scratch resistance.
Document 2 discloses that a novel environment-friendly phosphorus flame retardant additive added in an automobile leather flame retardant improves the flame retardant effect by 30%, and the ultra-high-speed constant-temperature emulsification technology is adopted to improve the stability of a liquid medicine from half a year to one year, so that the liquid medicine is more delicate to be a nano-scale emulsion and is more softly combined with leather.
At present, some existing leather flame-retardant coating technologies have the following characteristics:
the inorganic flame retardant is more and the organic flame retardant is less. The inorganic flame retardant has the advantages of low price and more varieties, has the defects of high specific gravity, large using amount, poor water resistance, poor compatibility and high mobility, and is used for adding flame retardance to leather finishing agents, so that the coating film has low strength, insufficient toughness, poor adhesion, poor decoration, reduced water resistance, high toxicological risk, time-dependent attenuation of flame retardant effect and the like. The organic flame retardant has the advantages of high flame retardant efficiency, small specific gravity, good water resistance and good compatibility, and has the disadvantages of less varieties, higher price, high toxicity, high halogen content and smoke, organic medium intolerance, environmental pollution caused by migration, and greater environmental pollution caused by high halogen content and smoke in fire.
② more additive flame retardants and less intrinsic flame retardants. The additive flame retardant is a low-molecular compound with a flame-retardant function, is added into the non-flame-retardant finishing agent in a blending mode, and has the advantages of multiple varieties, convenience in use and poor stability in the application process. The intrinsic flame retardant is formed by bonding elements with a flame retardant function into a molecular chain structure of a coating agent film forming material polymer in a chemical bond mode through molecular design and synthesis or synthesizing an element hybrid intrinsic flame retardant polymer to form a high molecular alloy in a physical blending mode.
Prior art documents:
document 1: chinese patent with application number of 201811429184.8, named as a water-based polyurethane-acrylate hybrid resin, a preparation method thereof and application thereof in leather finishing agents.
Document 2: the Chinese patent with the application number of 201911163050.0 is named as a flame retardant for automobile leather.
Disclosure of Invention
The invention aims to prepare a coating agent suitable for roller coating or spraying on the surface of leather, and the leather treated by the coating agent has synergistic composite functions of low toxicity, environmental protection, low smoke, zero halogen, long-acting flame retardance, water resistance, wear resistance, strong decoration, comfortable hand feeling and the like.
The invention discloses a phosphorus-boron heterochain prepolymer segmented polyurethane leather flame-retardant water-based coating agent, and a preparation method and application thereof.
In order to achieve the purpose, the technical scheme of the invention is as follows:
in a first aspect of the invention, a phosphorus boron heterochain prepolymer segmented polyurethane aqueous copolymer is disclosed, the structural formula of which is shown in formula (1):
in the formula (1), R includes-HCH2CH2OH、-(CH2CH2OH)2、-HCH2CH3、-(CH2CH3)2And the like.
In a second aspect of the present invention, a method for preparing the phosphorus boron heterochain prepolymer block polyurethane aqueous copolymer is disclosed, comprising the steps of:
(1) mixing an organic solvent, a phosphorus-boron hybrid chain prepolymer and dibutyltin dilaurate, then preserving heat under a protective atmosphere and a heating condition, adding toluene diisocyanate and dimethylolpropionic acid after the system temperature is uniform, and preserving heat after the system temperature is raised, and separating the solvent.
(2) And cooling the reaction system after the solvent is removed, adding a neutralizing agent and water, stirring, and adjusting the pH value of the system to obtain the catalyst.
In step (1), the organic solvent may include any one of xylene, toluene, cyclohexanone, and the like, and may be added in an amount sufficient to dissolve each raw material, and the present invention is not particularly limited.
Further, in the step (1), the viscosity of the phosphorus-boron heterochain prepolymer is 2000-2500 Cp (25 ℃), and optionally, the phosphorus-boron heterochain prepolymer is diluted by water to form a prepolymer diluent meeting the viscosity requirement.
Further, in the preparation method of the copolymer, the addition ratio of the phosphorus-boron heterochain prepolymer (PDCP-DGB), the Toluene Diisocyanate (TDI) and the dimethylolpropionic acid (DMPA) is as follows in sequence by mass percent: 75.9-76.9%, 16.2-17.3% and 6.8-6.9%.
In step (1), the mass ratio of dibutyltin dilaurate to toluene diisocyanate is 1: 0.01-0.03. In the present invention, the phosphorus boron heterochain prepolymer polyurethane block copolymer is synthesized by stepwise addition polymerization using the catalytic action of dibutyltin dilaurate.
Further, in the step (1), the number average molecular weight of the phosphorus-boron heterochain prepolymer is 800-1000, and the distribution index is 1.1-1.2.
Further, in the step (1), the protective atmosphere includes nitrogen, inert gas, and the like.
Further, in the step (1), the heating temperature is 60-65 ℃, the heating mode is water bath heating, and the heat preservation time is 20-35 min. The reaction at a certain temperature is helpful for accelerating the reaction rate and improving the reaction efficiency.
Further, in the step (1), the temperature of the system after being heated is 70-75 ℃, and the heat preservation time is 1.5-2.5 h.
Further, in the step (2), the neutralizing agent includes at least one of monoethanolamine, diethanolamine, monoethylamine, diethylamine, etc. In the invention, the main function of the neutralizer is to react with dimethylolpropionic acid in a system, and further regulate the pH value of a reaction product to be qualified.
Further, in the step (2), the temperature of the system is 45-50 ℃ after being cooled.
Further, in the step (2), the pH value is kept in the range of 7.5-9.0.
In the third aspect of the invention, the invention discloses a phosphorus-boron hybrid chain prepolymer block polyurethane leather flame-retardant water-based finishing agent, which comprises the following raw materials in percentage by mass: 11.5-13.5% of a coloring agent, 2.5-3.5% of carboxymethyl cellulose, 3.0-4.0% of a composite auxiliary agent and 80.0-82.0% of the phosphorus-boron heterochain prepolymer segmented polyurethane water-based copolymer.
Further, the colorant is an organic pigment or dye, which can be selected according to the actual leather color, and the invention is not particularly limited.
Further, the compound auxiliary agent is a mixture of a defoaming agent and a dispersing agent; optionally, the defoaming agent comprises at least one of tributyl phosphate, polymethyl silicone oil and the like, and the dispersing agent comprises at least one of OP-10, polyethylene glycol, sodium dodecyl benzene sulfonate and the like; optionally, the mass ratio of the defoaming agent to the dispersing agent is 1: 1-1: 2.
Furthermore, the fineness of the coating agent is less than or equal to 20 mu m, so that the coating agent can be uniformly coated on the surface of the leather.
Furthermore, the raw material composition of the coating agent also comprises a water composite solvent. Optionally, the addition amount of the water composite solvent is controlled to adjust the viscosity of the coating agent to be 120-150 s (coating-4 cups).
Further, the water composite solvent is a mixed system of water, ethanol and ethylene glycol dimethyl ether, and optionally, the volume ratio of the water, the ethanol and the ethylene glycol dibutyl ether is 3:1: 2.
In a fourth aspect of the present invention, a method for preparing the boron heterochain prepolymer block polyurethane leather flame-retardant water-based finishing agent is disclosed, which comprises the following steps: and uniformly mixing the colorant, the carboxymethyl cellulose, the composite auxiliary agent and the phosphorus-boron hybrid chain prepolymer block polyurethane aqueous copolymer, grinding, and then adjusting the viscosity by using a water composite solvent to obtain the product.
In a fifth aspect of the invention, the application of the boron-heterochain prepolymer segmented polyurethane leather flame-retardant water-based finishing agent in the preparation of leather products and the like is disclosed.
Compared with the prior art, the invention has the following beneficial effects:
(1) through molecular design and synthesis, the phosphorus-boron flame-retardant element and the hydrophilic group are bonded in a polyurethane molecular structure in a chemical bond form to obtain the phosphorus-boron heterochain prepolymer segmented polyurethane aqueous copolymer, and the copolymer has the characteristic of intrinsic flame retardance.
(2) The invention takes the boron hetero-chain hydroxyl-terminated prepolymer segmented polyurethane copolymer as a base material to prepare a finishing agent suitable for roller coating or spraying on the surface of leather, leather treated by the finishing agent has synergistic composite functions of low toxicity, environmental protection, low smoke, zero halogen, long-acting flame retardance, water resistance, wear resistance, strong decoration, comfortable hand feeling and the like, phosphorus and boron elements can ensure the long-acting flame retardance in a polyurethane molecular chain, and meanwhile, the boron hetero-chain hydroxyl-terminated prepolymer segmented polyurethane copolymer finishing agent has high elasticity, water resistance, wear resistance and soft hand feeling after being dried into a film.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out according to conventional conditions or according to conditions recommended by the manufacturers.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. The reagents or starting materials used in the present invention can be purchased from conventional sources, and unless otherwise specified, the reagents or starting materials used in the present invention can be used in a conventional manner in the art or in accordance with the product specifications. In addition, any methods and materials similar or equivalent to those described herein can be used in the methods of the present invention. The preferred methods and materials described herein are exemplary only, and the invention will now be further described with reference to specific embodiments.
In the following examples, the phosphorus-boron heterochain prepolymer is synthesized by the method disclosed in patent document No. 201710836186.8, the number average molecular weight is 800-1000, the distribution index is 1.1-1.2, and other conventional methods can be used to synthesize or purchase commercially available products.
In the following examples, the synthetic route of the phosphorus-boron heterochain prepolymer block polyurethane aqueous copolymer is shown as formula (2):
first embodiment
1. The preparation of the phosphorus-boron heterochain prepolymer block polyurethane aqueous copolymer comprises the following steps:
(1) 50ml of xylene, 45g of PDCP-DGB and dibutyltin dilaurate in a mass ratio of 1:0.01 to TDI were added to a four-necked flask with mechanical stirring, nitrogen protection, reflux condensation, water bath heating and a temperature control device.
(2) Stirring, introducing nitrogen, heating the reaction system obtained in the step (1) in a water bath to 60 +/-1 ℃, uniformly preserving the temperature of the system, dropwise adding 10.3g of TDI and 4.0g of DMPA within 30min, keeping the temperature of the system at 75 +/-1 ℃, preserving the temperature for 2h, and separating and recovering upper xylene.
(3) And (3) cooling the reaction system after removing the xylene through separation to 45 +/-1 ℃, then adding monoethanolamine and 50ml of water, continuing stirring for 1h, adjusting the pH to 9.0, and then adjusting the product viscosity to 2500Cp (25 ℃) through water to obtain the phosphorus-boron hybrid chain prepolymer segmented polyurethane aqueous copolymer diluent.
2. The preparation method of the phosphorus-boron hybrid chain prepolymer block polyurethane leather flame-retardant water-based finishing agent comprises the following steps:
s1, weighing 80.0g of phosphorus-boron hybrid chain prepolymer segmented polyurethane aqueous copolymer diluent prepared in the embodiment, 13.5g of red aqueous color paste, 3.5g of carboxymethyl cellulose and 3.0g of composite auxiliary agent (a mixture of tributyl phosphate and OP-10 in a mass ratio of 1: 1), adding the mixture into a mixing container, stirring and mixing, adding 15ml of water composite solvent (a mixture of water, ethanol and ethylene glycol dibutyl ether in a volume ratio of 3:1: 2), stirring uniformly, pouring the obtained mixed solution into a sand mill, starting the sand mill, keeping the rotating speed at 5000r/min and the cooling water temperature at or below 30 ℃, and grinding for 30 min;
and S2, detecting and grinding the mixture by using a fineness scraper to the fineness of less than or equal to 20 mu m, adding a water composite solvent (a mixture of water, ethanol and ethylene glycol dibutyl ether in a volume ratio of 3:1: 2), continuously grinding for 5min, adjusting the viscosity of the coating agent to 140S (coating-4 cups), stopping a sand mill, filtering and discharging to obtain the phosphorus-boron hybrid chain prepolymer block polyurethane leather flame-retardant water-based coating agent.
Second embodiment
1. The preparation of the phosphorus-boron heterochain prepolymer block polyurethane aqueous copolymer comprises the following steps:
(1) 50ml of xylene, 46.1g of PDCP-DGB and dibutyltin dilaurate in a mass ratio of TDI to TDI of 1:0.03 were added to a four-neck flask with mechanical stirring, nitrogen protection, reflux condenser, water bath heating and a temperature control device.
(2) Stirring, introducing nitrogen, heating the reaction system obtained in the step (1) in a water bath to 65 +/-1 ℃, uniformly preserving the temperature of the system, dropwise adding 9.7g of TDI and 4.1g of DMPA within 30min, keeping the temperature of the system at 75 +/-1 ℃, preserving the temperature for 1.5h, and separating and recovering upper xylene.
(3) And (3) cooling the reaction system after removing the xylene through separation to 45 +/-1 ℃, then adding monoethanolamine and 50ml of water, continuing stirring for 1h, adjusting the pH to 8.0, and then adjusting the product viscosity to 2200Cp (25 ℃) through water to obtain the phosphorus-boron hybrid chain prepolymer segmented polyurethane aqueous copolymer diluent.
2. The preparation method of the phosphorus-boron hybrid chain prepolymer block polyurethane leather flame-retardant water-based finishing agent comprises the following steps:
s1, weighing 82.0g of phosphorus-boron hybrid chain prepolymer segmented polyurethane aqueous copolymer diluent prepared in the embodiment, 11.5g of yellow aqueous color paste, 2.5g of carboxymethyl cellulose and 4.0g of composite auxiliary agent (a mixture of tributyl phosphate and OP-10 in a mass ratio of 1: 2), adding the mixture into a mixing container, stirring and mixing, adding 15ml of water composite solvent (a mixture of water, ethanol and ethylene glycol dibutyl ether in a volume ratio of 3:1: 2), stirring uniformly, pouring the obtained mixed solution into a sand mill, starting the sand mill, keeping the rotating speed at 5000r/min and the cooling water temperature at or below 30 ℃, and grinding for 30 min;
and S2, detecting and grinding the mixture by using a fineness scraper to the fineness of less than or equal to 20 mu m, adding a water composite solvent (a mixture of water, ethanol and ethylene glycol dibutyl ether in a volume ratio of 3:1: 2), continuously grinding for 5min, adjusting the viscosity of the coating agent to be 120S (coating-4 cups), stopping a sand mill, filtering and discharging to obtain the phosphorus-boron hybrid chain prepolymer block polyurethane leather flame-retardant water-based coating agent.
Third embodiment
1. The preparation of the phosphorus-boron heterochain prepolymer block polyurethane aqueous copolymer comprises the following steps:
(1) 50ml of xylene, 45.8g of PDCP-DGB and dibutyltin dilaurate in a mass ratio of TDI to TDI of 1:0.02 were added to a four-neck flask with mechanical stirring, nitrogen protection, reflux condenser, water bath heating and a temperature control device.
(2) Stirring, introducing nitrogen, heating the reaction system obtained in the step (1) in a water bath to 60 +/-1 ℃, uniformly preserving the temperature of the system, dropwise adding 10.0g of TDI and 4.0g of DMPA within 30min, keeping the temperature of the system at 70 +/-1 ℃, preserving the temperature for 2.5h, and separating and recovering upper xylene.
(3) And (3) cooling the reaction system after removing the xylene through separation to 50 +/-1 ℃, then adding monoethanolamine and 50ml of water, continuing stirring for 1h, adjusting the pH to 7.5, and then adjusting the product viscosity to 2000Cp (25 ℃) by using water to obtain the phosphorus-boron hybrid chain prepolymer segmented polyurethane aqueous copolymer diluent.
2. The preparation method of the phosphorus-boron hybrid chain prepolymer block polyurethane leather flame-retardant water-based finishing agent comprises the following steps:
s1, weighing 81.0g of phosphorus-boron hybrid chain prepolymer segmented polyurethane aqueous copolymer diluent prepared in the embodiment, 12.5g of blue aqueous color paste, 3.0g of carboxymethyl cellulose and 3.5g of composite auxiliary agent (a mixture of tributyl phosphate and OP-10 in a mass ratio of 1: 1), adding the mixture into a mixing container, stirring and mixing, adding 15ml of water composite solvent (a mixture of water, ethanol and ethylene glycol dibutyl ether in a volume ratio of 3:1: 2), stirring uniformly, pouring the obtained mixed solution into a sand mill, starting the sand mill, keeping the rotating speed at 5000r/min and the cooling water temperature at or below 30 ℃, and grinding for 30 min;
and S2, detecting and grinding the mixture by using a fineness scraper to the fineness of less than or equal to 20 mu m, adding a water composite solvent (a mixture of water, ethanol and ethylene glycol dibutyl ether in a volume ratio of 3:1: 2), continuously grinding for 5min, adjusting the viscosity of the coating agent to be 150S (coating-4 cups), stopping a sand mill, filtering and discharging to obtain the phosphorus-boron hybrid chain prepolymer block polyurethane leather flame-retardant water-based coating agent.
Performance testing
The performance of the film coating agent prepared by using the phosphorus-boron hybrid prepolymer polyurethane segmented copolymer in the above embodiment is tested by the specific methods of QB/T2710-2018, GB/T5454-1997 and GB/T4689.21-2008, and the results of the measured performance indexes are shown in Table 1.
TABLE 1
| Sample (I) | Tensile Strength (MPa) | LOI | Water absorption (%) |
| Commercial unpainted treated artificial leather | 7 | 17.0 | 40 |
| Finishing treatment of Artificial leather (first embodiment) | 8 | 27.0 | 25 |
| Finishing treatment of Artificial leather (second embodiment) | 9 | 29.0 | 26 |
| Finishing treatment of Artificial leather (third embodiment) | 8 | 28.0 | 25 |
As can be seen from Table 1, after the finishing agent prepared in the examples is used for treating, the tensile strength, the flame-retardant oxygen index and the water resistance of the commercial uncoated artificial leather are obviously improved.
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2307208C1 (en) * | 2006-05-26 | 2007-09-27 | Государственное образовательное учреждение высшего профессионального образования Волгоградский государственный технический университет (ВолгГТУ) | Simulated leather |
| CN107573479A (en) * | 2017-09-25 | 2018-01-12 | 天津科技大学 | Utilize the preparation method of the intrinsic modified aqueous polyurethane of phosphorus flame retardant |
| RU2647912C1 (en) * | 2017-04-10 | 2018-03-21 | АКЦИОНЕРНОЕ ОБЩЕСТВО "РУССКАЯ КОЖА" (АО "Русская кожа") | Method of producing heat-resistant leather |
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- 2020-11-20 CN CN202011311404.4A patent/CN112480348A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
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| RU2307208C1 (en) * | 2006-05-26 | 2007-09-27 | Государственное образовательное учреждение высшего профессионального образования Волгоградский государственный технический университет (ВолгГТУ) | Simulated leather |
| RU2647912C1 (en) * | 2017-04-10 | 2018-03-21 | АКЦИОНЕРНОЕ ОБЩЕСТВО "РУССКАЯ КОЖА" (АО "Русская кожа") | Method of producing heat-resistant leather |
| CN107573479A (en) * | 2017-09-25 | 2018-01-12 | 天津科技大学 | Utilize the preparation method of the intrinsic modified aqueous polyurethane of phosphorus flame retardant |
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