CN110922860B - 一种针对易挥发性酸的环保型气敏涂料及其制备方法 - Google Patents

一种针对易挥发性酸的环保型气敏涂料及其制备方法 Download PDF

Info

Publication number
CN110922860B
CN110922860B CN201911254671.XA CN201911254671A CN110922860B CN 110922860 B CN110922860 B CN 110922860B CN 201911254671 A CN201911254671 A CN 201911254671A CN 110922860 B CN110922860 B CN 110922860B
Authority
CN
China
Prior art keywords
parts
color
agent
changing
coating
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.)
Active
Application number
CN201911254671.XA
Other languages
English (en)
Other versions
CN110922860A (zh
Inventor
冯圣玉
吴连锋
王贤明
卢海峰
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shandong University
Original Assignee
Shandong University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Shandong University filed Critical Shandong University
Priority to CN201911254671.XA priority Critical patent/CN110922860B/zh
Publication of CN110922860A publication Critical patent/CN110922860A/zh
Priority to EP21194838.5A priority patent/EP3960746A1/en
Priority to EP20178120.0A priority patent/EP3831835A1/en
Application granted granted Critical
Publication of CN110922860B publication Critical patent/CN110922860B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • 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
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
    • C08G18/6225—Polymers of esters of acrylic or methacrylic acid
    • C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
    • 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
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C08G59/4246—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof polymers with carboxylic terminal groups
    • C08G59/4269—Macromolecular compounds obtained by reactions other than those involving unsaturated carbon-to-carbon bindings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
    • C09B67/0083—Solutions of dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
    • C09B67/0084—Dispersions of dyes
    • C09B67/0085—Non common dispersing agents
    • C09B67/009—Non common dispersing agents polymeric dispersing agent
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
    • C09B67/0092—Dyes in solid form
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B69/00—Dyes not provided for by a single group of this subclass
    • C09B69/008—Dyes containing a substituent, which contains a silicium atom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/0081—Composite particulate pigments or fillers, i.e. containing at least two solid phases, except those consisting of coated particles of one compound
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/28—Compounds of silicon
    • C09C1/30—Silicic acid
    • C09C1/3081—Treatment with organo-silicon compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/36—Compounds of titanium
    • C09C1/3607—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/36—Compounds of titanium
    • C09C1/3607—Titanium dioxide
    • C09C1/3684—Treatment with organo-silicon compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/40—Compounds of aluminium
    • C09C1/405—Compounds of aluminium containing combined silica, e.g. mica
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/40—Compounds of aluminium
    • C09C1/407—Aluminium oxides or hydroxides
    • 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
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • 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
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C09D163/04—Epoxynovolacs
    • 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
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/06—Polyurethanes from polyesters
    • 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
    • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
    • 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
    • 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
    • C09D7/41—Organic pigments; Organic dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2217—Oxides; Hydroxides of metals of magnesium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2251—Oxides; Hydroxides of metals of chromium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2265—Oxides; Hydroxides of metals of iron
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Composite Materials (AREA)
  • Paints Or Removers (AREA)

Abstract

本发明涉及一种针对易挥发性酸的环保型气敏涂料及其制备方法，包括如下质量份的组分：耐强酸树脂50‑100份、特种变色剂A 1‑30份、辅助变色组分0.5‑5份、填料0‑20份、助剂0‑20份、溶剂0‑300份；所述的特种变色剂A为化合物B对白炭黑处理后得到的物质。本发明利用特种变色剂A遇酸性气体变色的性能，通过辅助变色组分对颜色变化进行强化，结合颜料、填料、助剂等的合理配伍，实现针对挥发性酸的气敏涂料的制备。本发明具有变色明显、变色迅速、变色可逆、配套性好等特点，适用于制造、储存、运输和使用强酸的装置表面。石油烷基化、氟化工行业、矿石浮选、纸浆和造纸行业、半导体行业等制造行业，市场需求前景好。

Description

一种针对易挥发性酸的环保型气敏涂料及其制备方法
技术领域
本发明涉及一种针对易挥发性酸的气敏涂料的研制，属于化工产品综合利用领域。
背景技术
浓硫酸、氢氟酸、硝酸、盐酸等强酸在石油烷基化、氟化工行业、矿石浮选、纸浆和造纸行业、半导体行业等化工生产中有广泛的应用，为推动国民经济发展做出了巨大贡献。目前，石油化工行业传统的烷基化工艺有两种，分别为氢氟酸法和硫酸法。氢氟酸法是以氢氟酸作为催化剂，将异丁烷与丁烯合成工业异辛烷(即烷基化油)的过程。所制备的烷基化油是异构烷烃的混合物，不仅抗爆性好、无铅汽油辛烷值高达94以上，而且具有理想的挥发性能和洁净的燃烧性能，是车用汽油的理想组分。在氢氟酸烷基化工艺中，氢氟酸是最重要的原料之一。烷基化装置的氢氟酸输送管道法兰连接处等位置，均是潜在泄漏点，一旦发生泄漏，将会带来巨大的危害。氢氟酸具有极强的腐蚀性，对含硅材料(玻璃、水泥等)和各种金属设备破坏性极大；氢氟酸暴露于空气中时极易挥发，味道极小，且无色，很难被人们察觉，但是会对人、动物造成严重且无法愈合的伤害，甚至危及生命安全。因此，尽早发现氢氟酸的泄露是非常重要，可极大地减小氢氟酸泄漏造成的伤害。
遇氢氟酸变色警示涂料是专门用来检测氢氟酸/氟化氢蒸汽是否泄漏的特种专用涂料，是一类针对易挥发性酸的气敏性涂料。涂装于氢氟酸输送管道法兰或阀门上，正常情况下起到防腐作用，一旦发生氢氟酸泄漏时，可在短时间内发生显著的颜色变化，变色迅速、持久，可起到有效的警示作用，便于对泄漏部位及时处理，防止重大安全事故的发生。
与氢氟酸类似，盐酸、硝酸、冰乙酸等工业用酸均存在易挥发、易泄漏、无色、危害性大等严重问题，迫切需要研制针对易挥发性酸的气敏涂料。由于溶剂型涂料在涂装过程中有挥发性有机物释放，对空气造成污染，因此，研制环保的无溶剂气敏涂料更加符合社会发展需求。
中国专利文件CN106905833A(申请号201710218911.5)提供了一种环保变色的内墙涂料及其制备方法。该涂料组分包括:聚氨酯树脂材料、乙醇、抗收缩剂、三苯甲烷类染料或荧烷染料。该涂料可以有效地警示对人体健康不利的过酸或过碱环境，使人能及时保持工作环境空气流通，采取积极的防护措施。但是其选用的聚氨酯树脂不耐强酸，遇到强酸泄漏时会产生涂料分解和脱落，不能对设备进行保护。
中国专利文件CN108530053A(申请号：201810279464.9)公开了一种pH值敏感变色无机材料及其制备方法，将所制备得到的pH值敏感变色粉体与其他树脂溶液或乳液混合可获得pH值敏感的变色涂料或膜材料。其制备的pH值敏感变色无机材料制备过程步骤较多，耗能较高。
国外对于遇酸警示涂料的研究虽然较早，但也仅数家公司成功开发，并已在石化装置、氟化工行业、半导体行业等获得广泛应用。由于研制难度较大，国内遇酸警示涂料的研究较少。上世纪90年代，我国曾研制出一款“氟化氢指示漆”，但与国外产品相比，存在变色不明显、变色时间长、变色不可逆(只能一次性使用)等问题，应用大大受限。目前，国内使用的遇酸警示涂料基本依赖进口，存在价格高、供货周期长等问题。而且目前国外产品为溶剂型涂料，需要使用溶剂型涂料稀释，不环保，不能实现环保涂装。
综上所述，目前行业内迫切需要一种环保型遇酸变色的气敏涂料，特别是针对氢氟酸、盐酸、硝酸、冰乙酸等挥发性酸的气敏涂料。
发明内容
针对国内外现有的遇酸警示涂料技术的不足，本发明提供一种针对氢氟酸、盐酸、硝酸、冰乙酸等挥发性酸的气敏涂料，该涂料配方简单、制备容易，便于进行工业化生产。该涂料具有变色迅速、变色明显及变色可逆的特点并且能够与环氧、丙烯酸、聚氨酯等多种涂层配套使用，广泛应用于石油化工行业装置中管道法兰连接处、储存罐封口等部位，检测氢氟酸等挥发性酸是否发生泄漏，起到及时报警作用。
发明概述
本发明提供的一种针对易挥发性酸的环保型气敏涂料，以双组份无溶剂耐强酸树脂作为成膜物质，加入特种变色剂、辅助变色组分填料、助剂等，制备得到涂料混合物。该混合物涂装后，变色明显、迅速，能够起到快速示警作用，且变色可逆，能反复使用；该涂料可与环氧、丙烯酸、聚氨酯等绝大多数涂层配套使用，应用面广。
发明详述
本发明的技术方案如下：
一种针对易挥发性酸的环保型气敏涂料，包括如下质量份的组分：
耐强酸树脂50-100份、特种变色剂A1-30份、辅助变色组分0.5-5份、填料0-20份、助剂0-20份、溶剂0-300份；
所述的特种变色剂A为化合物B对白炭黑处理后得到的物质；
所述的化合物B，具有如下的结构特征：
Figure BDA0002307743080000031
其中：R′为各种起桥联作用的有机基团，将苯环与硅原子进行连接；进一步优选为亚烷基，更优选C1-C8的亚烷基，优选亚甲基、亚乙基或亚丙基；
R″为各种能够以HOR″结构离去的有机基团；进一步优选为烷基或芳基，更优选C1-C8的烷基或苯基，优选甲基、乙基、异丙基、叔丁基或苯基。
根据本发明，优选的，所述的耐强酸树脂包括各种耐强酸的双组分无溶剂树脂；进一步优选为无溶剂环氧树脂、无溶剂酚醛环氧树脂、无溶剂聚氨酯树脂、无溶剂聚脲树脂；更优选为无溶剂聚氨酯树脂。
根据本发明，所述的白炭黑为各种市售的白炭黑商品，包括各种沉淀法白炭黑和气相法白炭黑，优选沉淀法白炭黑。
根据本发明，优选的，所述的化合物B，按如下方法制备得到：
选择带有化合物B分子中R′基团左边结构的化合物通过化学修饰过程，使其具备反应活性，进而使该活化的化合物与硅烷进行反应，得到化合物B。
根据本发明，优选的，所述的化合物B分子中R′基团左边结构的化合物为甲基橙或甲基橙衍生物。
根据本发明，优选的，上述化学修饰过程，包括但不限于：酰氯化、环氧官能化、羟基官能化、羧基官能化等常见化学修饰反应。
根据本发明，优选的，上述硅烷，包括但不限于市场上所能够采购到的各种硅烷偶联剂及小分子硅烷化合物，包括氨丙基三甲氧基硅烷、氨丙基三乙氧基硅烷、氯丙基三乙氧基硅烷、氯丙基三甲氧基硅烷、三甲基一氯硅烷、二甲基二氯硅烷、甲基三氯硅烷、四氯硅烷、二甲基一氢一氯硅烷等化合物。
根据本发明，上述过程未直接描述的、但是能够从市售产物中获得特种变色剂A的制备过程也在本发明的范围之内。
根据本发明，优选的，化合物B对白炭黑处理过程如下：
将化合物B与白炭黑及溶剂进行共混，升温至溶剂进行回流，保持反应2-4小时，停止回流。随后减压蒸除溶剂，得到特种变色剂A。
上述的白炭黑包括市售的各种气相法白炭黑、沉淀法白炭黑；优选沉淀法白炭黑；
上述的溶剂包括各种市售的能够溶解化合物B、同时不与化合物B及白炭黑进行反应的有机溶剂，优选甲苯、四氢呋喃、丙酮；进一步优选甲苯。
根据本发明，优选的，所述的辅助变色组分包括各种能够提高涂料色泽亮度并辅助特种变色剂A进行变色显示的组分，包括各种有机染料和无机颜料；进一步优选为改性聚苯胺、中铬黄、永固黄、耐晒黄、锌黄、柠檬黄、铁棕、铁黄等；更优选中铬黄和永固黄三者的混合物。
根据本发明，优选的，所述的填料是用来提高涂料机械力学性能等基础性能的填料，包括二氧化钛、云母粉、氢氧化铝、氢氧化镁、硅微粉、白炭黑、滑石粉、纳米碳酸钙、硫酸钡；进一步优选为二氧化钛、云母粉和氢氧化铝的混合物。
根据本发明，优选的，所述的助剂为能够提高涂料性能的各种试剂，包括流平剂、消泡剂、分散剂、防沉降剂。
根据本发明，优选的，耐强酸树脂、特种变色剂A、辅助变色组分、填料、助剂的质量比为100：1-30：0.5-5：0-20：0-40；进一步优选为100：5-20：10-20：15-30：1-5。
根据本发明，优选的，所述的针对易挥发性酸的环保型气敏涂料还包括25质量份的固化剂；进一步优选的，所述的固化剂为异氰酸酯固化剂或聚酰胺树脂。
根据本发明，上述针对易挥发性酸的环保型气敏涂料的其制备方法，包括步骤如下：
按重量比将耐强酸树脂、特种变色剂A、辅助变色组分、填料、助剂、溶剂进行混合，搅拌分散均匀，然后研磨至细度小于40微米，得到涂料A组分。
根据本发明，优选的，将固化剂作为涂料B组分，将涂料A组分、涂料B组分按4～5：1质量比混合固化，得到针对易挥发性酸的环保型气敏涂料。
本发明未详尽说明的，均按现有技术。
本发明的原理及有益效果如下：
气敏警示涂料的作用是当有酸性气体泄漏时，涂料与酸性气体发生反应，及时变色起到警示和报警的作用。
本发明的原理是利用特种变色剂A遇酸性气体变色的性能，通过辅助变色组分对颜色变化进行强化，结合颜料、填料、助剂等的合理配伍，实现针对挥发性酸的气敏涂料的制备。
本发明所述的特种变色剂A能够与强酸性气体相互作用从而变色。一般市售的酸碱指示剂也可以实现遇酸变色的目的。但是市售的酸碱指示剂一般为有机弱酸弱碱类小分子，加工成涂料后，容易产生遇水流失、褪色的严重问题，甚至能导致涂料的降解和脱落。本发明制备的特种变色剂A是通过化学反应将变色基团固定在白炭黑的表面，从而保证了后续制备的材料在经历多次水洗后不会溶于水从而流失(即不会产生褪色)的效果。因此，优于市售的酸碱指示剂。
本发明所述的特种变色剂A常态下颜色较淡，在遇强酸后显示深红色。为了提高变色剂A的颜色警示作用，本发明选择改性聚苯胺、中铬黄和永固黄的混合物将涂料遇酸前的颜色调至亮黄色。由此造成了涂料在遇酸前呈现亮黄色、遇酸后呈现深红色的效果。选用其它颜色的颜料组分也能够提高特种变色剂A的变色效果。但从实际工厂应用来看，改性聚苯胺、中铬黄和永固黄的混合配比效果最佳。
本发明所述的填料能够提高涂料机械力学性能等基础性能。比如，云母粉可以进行补强并提高涂料硬度；氢氧化铝能够进行补强并提高涂料阻燃性；二氧化钛能够进行补强并提高耐候性、白炭黑能够进行补强并提高涂料表面的疏水性等。具体根据涂料的不同应用需求对填料进行筛选。按照目前工厂应用工况来看，优选为二氧化钛、云母粉和氢氧化铝的混合物。
本发明所述的助剂为能够提高涂料性能的各种助剂。比如，流平剂有利于涂料在设备表面形成平整的膜；消泡剂能够消除涂料在施工时起泡，提高涂层致密度并减少缺陷等。
本发明的有益效果：
本发明制备了一种针对挥发性酸的、变色明显、变色迅速且变色可逆的环保型遇酸警示涂料。以耐强酸树脂为基体树脂，加入特种变色剂、辅助变色组分、颜填料、助剂等，制备的气敏涂料，具有如下特点：
1.变色明显--遇酸后由黄色变为红色。
2.变色迅速--变色时间小于1S。
3.变色可逆--变色后经水冲洗可恢复，能反复使用。
4.配套性好。
本发明所研制的涂料适用于pH＜3的酸或酸性气体，包括氢氟酸(液体或蒸汽)、硫酸、氟硅酸、盐酸、硝酸、氯、氢溴酸、三氟乙酸、高氯酸、冰醋酸、其他酸或酸蒸汽。
适用于制造、储存、运输和使用强酸的装置表面。
石油烷基化、氟化工行业、矿石浮选、纸浆和造纸行业、半导体行业等制造行业，市场需求前景好。
附图说明
图1为实施例1制得的化合物B1的红外光谱图。
图2为实施例1中制得的特种变色剂A1的红外光谱图。
图3为试验例1中测试胶片在氢氟酸溶液中的颜色变化图。
图4为试验例1中测试胶片在硝酸、盐酸、冰乙酸、甲酸中的颜色变化图。
图5为试验例3中变色后的测试胶片经水浸泡去除表面氢氟酸后的颜色变化图。
图6为试验例4中本发明与国外产品的性能对比图。
具体实施方式
下面通过具体实施例对本发明做进一步说明，但不限于此。
实施例中所用原料均为常规市购原料或按照参考文献方法合成得到。
实施例中所述的分子量均为数均分子量。实施例中所述的份数均为重量份。
实施例中所用的BYK410、BYK180为一种防沉助剂，可以保持各种无机填料在涂料体系中实现均匀分散，不发生沉降，产生不可搅起的硬块，市购产品。
实施例1
在氩气保护下，将20g甲基橙加入到100mL无水四氢呋喃溶液中，随后逐滴加入20mL二甲酰氯，室温搅拌下反应2小时。蒸馏除去溶剂后，往反应体系再次加入100mL无水四氢呋喃溶液，随后加入过量的氨丙基三乙氧基硅烷，室温搅拌3小时。先蒸馏除去溶剂，随后减压蒸除未反应的氨丙基三乙氧基硅烷，得到带硅烷氧基基团的官能化的甲基橙化合物。记为化合物B1。反应路线如下所示：
Figure BDA0002307743080000061
对化合物B1进行分析表征，红外谱图如图1所示。
将10g化合物B1、50g沉淀法白炭黑和200mL甲苯共混，升温至甲苯回流，保持回流状态2小时。停止回流，蒸除甲苯，得到特种变色剂A1。
对特种变色剂A1进行红外分析，谱图如图2所示。
实施例2
称量E51环氧树脂60份、6份二氧化钛、16份云母粉、5份氢氧化铝、3份改性聚苯胺、15份变色剂A1；10份中铬黄、8份永固黄、1份BYK410、1份BYK180进行初步混合，使用高速分散机搅拌分散30分钟，然后将涂料使用三辊机研磨至细度小于40微米时，出料包装，得到气敏涂料A组分，涂料B组分为300#聚酰胺固化剂40份，A、B组分按质量比5：1比例固化得到气敏涂料。
实施例3
称量80份无溶剂酚醛环氧树脂、9份二氧化钛、10份云母粉、10份氢氧化铝、3份改性聚苯胺、15份变色剂A1；5份中铬黄、5份永固黄、1份BYK410、1份BYK180进行初步混合，使用高速分散机搅拌分散30分钟，然后将涂料转移至篮式砂磨机，研磨至细度小于40微米时，出料包装，得到涂料A组分，涂料B组分为无溶剂改性芳香胺固化剂20份，A、B组分按质量比5：1比例固化得到气敏涂料。
实施例4
称量80份羟基丙烯酸树脂、6份二氧化钛、20份云母粉、15份氢氧化铝、3份改性聚苯胺、15份变色剂A1、5份中铬黄、5份永固黄、1份BYK410、1份BYK180进行初步混合，使用高速分散机搅拌分散30分钟，然后将涂料转移至篮式砂磨机，研磨至细度小于40微米时，出料包装得到涂料A组分，B组分选用异氰酸酯预聚物N3300为固化剂20份，A、B组分按质量比4：1比例固化得到气敏涂料。
实施例5
称量82.5份羟基丙烯酸树脂、6份二氧化钛、16份云母粉、5份氢氧化铝、3份改性聚苯胺、15份变色剂A1；10份中铬黄、8份永固黄、1份BYK410、1份BYK180进行初步混合，使用高速分散机搅拌分散30分钟，然后将涂料转移至篮式砂磨机，研磨至细度小于40微米时，出料包装得到涂料A组分，B组分选用异氰酸酯预聚物N3300为固化剂18.5份，A、B组分按质量比4：1比例固化得到气敏涂料。
实施例6
称量70份羟基聚酯树脂、6份二氧化钛、16份云母粉、5份氢氧化铝、3份改性聚苯胺、15份变色剂A2；10份中铬黄、8份永固黄、1份BYK410、1份BYK180进行初步混合，使用高速分散机搅拌分散30分钟，然后将涂料转移至篮式砂磨机，研磨至细度小于40微米时，出料包装得到涂料A组分，B组分选用异氰酸酯预聚物N3390为固化剂30份，A、B组分按质量比3：1比例固化得到气敏涂料。
实施例7
称量80份羟基聚酯树脂、6份二氧化钛、16份云母粉、5份氢氧化铝、3份改性聚苯胺、15份变色剂A2；10份中铬黄、8份永固黄、1份BYK410、1份BYK180进行初步混合，使用高速分散机搅拌分散30分钟，然后将涂料转移至篮式砂磨机，研磨至细度小于40微米时，出料包装得到涂料A组分，B组分选用异氰酸酯预聚物N3390为固化剂20份，A、B组分按质量比3：1比例固化得到气敏涂料。
实施例8
称量85份羟基丙烯酸树脂、6份二氧化钛、16份云母粉、5份氢氧化铝、3份改性聚苯胺、15份变色剂A2；10份中铬黄、8份永固黄、1份BYK410、1份BYK180进行初步混合，使用高速分散机搅拌分散30分钟，然后将涂料转移至篮式砂磨机，研磨至细度小于40微米时，出料包装得到涂料A组分，B组分选用异氰酸酯预聚物N3300为固化剂15份，A、B组分按质量比3：1比例固化得到气敏涂料。
实施例9
称量75份天门冬氨酸树脂、6份二氧化钛、16份云母粉、5份氢氧化铝、3份改性聚苯胺、15份变色剂A3；10份中铬黄、8份永固黄、1份BYK410、1份BYK180进行初步混合，使用高速分散机搅拌分散30分钟，然后将涂料转移至篮式砂磨机，研磨至细度小于40微米时，出料包装得到涂料A组分，B组分选用异氰酸酯预聚物N3390为固化剂25份，A、B组分按质量比4：1比例固化得到气敏涂料。
实施例10
称量40份羟基聚酯树脂、40份羟基丙烯酸树脂，6份二氧化钛、16份云母粉、5份氢氧化铝、3份改性聚苯胺、15份变色剂A3；10份中铬黄、8份永固黄、1份BYK410、1份BYK180进行初步混合，使用高速分散机搅拌分散30分钟，然后将涂料转移至篮式砂磨机，研磨至细度小于40微米时，出料包装得到涂料A组分，B组分选用异氰酸酯预聚物N3300为固化剂20份，A、B组分按质量比4：1比例固化得到气敏涂料。
实施例11
称量50份羟基丙烯酸树脂、30份羟基聚酯树脂、6份二氧化钛、16份云母粉、5份氢氧化铝、3份改性聚苯胺、15份变色剂A3；10份中铬黄、8份永固黄、1份BYK410、1份BYK180进行初步混合，使用高速分散机搅拌分散30分钟，然后将涂料转移至篮式砂磨机，研磨至细度小于40微米时，出料包装得到涂料A组分，B组分选用异氰酸酯预聚物N3300为固化剂20份，A、B组分按质量比4：1比例固化得到气敏涂料。
试验例1
将涂料喷涂或刷涂于聚四氟乙烯薄板上，室温下固化7d，形成厚度为1.5±0.5mm的胶片。测试了上述实施例中涂料的拉伸强度，结果如表1所示。
表1
编号 漆膜拉伸强度(MPa) 断裂伸长率(％)
实施例2 18.5 3
实施例3 19.7 5
实施例4 14.0 18
实施例5 17.0 22
实施例6 23.1 26
实施例7 26.6 35
实施例8 27.2 10
实施例9 28.0 30
实施例10 22.2 16
实施例11 18.0 31
由表1可以看出，添加变色剂A后，涂料的拉伸强度和断裂伸长率均较高，未对涂料拉伸强度、断裂伸长率等性能产生劣化影响，符合使用要求。
试验例2
测试上述实施例中涂料的遇氢氟酸的变色性能，不同的实施例中涂层变色时间及颜色变化情况见表2。
表2
编号 变色时间 变色程度
实施例2 6s 黄色变为红色
实施例3 5s 黄色变为红色
实施例4 2s 黄色变为深红色
实施例5 5s 黄色变为浅红色
实施例6 8s 黄色变为红色
实施例7 5s 黄色变为红色
实施例8 2s 黄色变为红色
实施例9 1s 黄色变为浅红色
由表2可知，本发明的遇酸变色警示涂料遇酸后变色迅速，最快在1s内就可有变色反应。而且变色由黄色变为红色，前后颜色变化明显，易于察觉而起到警示作用。
将上述树脂拉伸强度测试胶片浸泡于氢氟酸溶液中，颜色变化如图3所示。由图3可知，测试胶片黄色变成红色，颜色变化明显。
测试胶片在硝酸、盐酸、冰乙酸、甲酸中的颜色变化如图4所示，由图4可知，在上述酸中测试胶片均由黄色变为红色，颜色变化明显。
试验例3
测试上述实施例中涂料的变色可逆性能，将变色后的涂层经水浸泡等方式去除表面氢氟酸后，观察颜色变化情况。结果如图4所示。
由图4可知，变色后的涂层经水浸泡等方式去除表面氢氟酸后，涂层由红色恢复为黄色。经试验验证，恢复为黄色的涂层遇氢氟酸后又变为红色，表明该涂层变色具有可逆性，经验证，可反复使用10次以上。本发明的涂料颜色变化具有良好的可逆性。
试验例4
测试本发明涂料与市购国外产品和国内产品的性能，结果如表3、图5所示。图5中，1#为国外遇液体氢氟酸变色警示涂料，2#3#为本发明遇液体氢氟酸变色警示涂料。
表3
指标 国外产品 本产品 国内其他产品
变色程度 黄色→红色 黄色→红色 橙黄色→黄色
变色时间 ＜1s ＜1s ＞1h
是否可逆 是 是 否
由表3、图5可知，本发明的气敏涂料性能优于国内同类产品。与国外产品相比，颜色变化、变色时间和可逆性类似，但是本发明涂料颜色变化更加明显、深艳。而且本发明制备成本明显低于国外产品。例如：国外产品价格大约在600-1000元/公斤，本发明成本大约在150-200元/公斤。因此，本发明提供了性能优越、成本低廉的遇酸变色气敏涂料，而且降低了生产周期，打破了国外的技术垄断。

Claims (13)

1.一种针对易挥发性酸的环保型气敏涂料，其特征在于，该气敏涂料包括如下质量份的组分：
耐强酸树脂50-100份、特种变色剂A 1-30份、辅助变色组分0.5-5份、填料0-20份、助剂0-20份、溶剂0-300份；
所述的特种变色剂A 为化合物B对白炭黑处理后得到的物质；
所述的化合物B，具有如下的结构特征：
Figure DEST_PATH_IMAGE002
其中：R′为各种起桥联作用的有机基团，将苯环与硅原子进行连接；
R″为各种能够以HOR″结构离去的有机基团。
2.根据权利要求1所述的针对易挥发性酸的环保型气敏涂料，其特征在于，所述的耐强酸树脂为耐强酸的双组分无溶剂树脂。
3.根据权利要求1所述的针对易挥发性酸的环保型气敏涂料，其特征在于，所述的耐强酸树脂为无溶剂环氧树脂、无溶剂聚氨酯树脂或无溶剂聚脲树脂。
4.根据权利要求1所述的针对易挥发性酸的环保型气敏涂料，其特征在于，所述的辅助变色组分为能够提高涂料色泽亮度并辅助特种变色剂A进行变色显示的有机染料或无机颜料。
5.根据权利要求1所述的针对易挥发性酸的环保型气敏涂料，其特征在于，所述的辅助变色组分为改性聚苯胺、中铬黄、永固黄、耐晒黄、锌黄、柠檬黄、铁棕或铁黄。
6.根据权利要求1所述的针对易挥发性酸的环保型气敏涂料，其特征在于，所述的填料是二氧化钛、云母粉、氢氧化铝、氢氧化镁、硅微粉、白炭黑、滑石粉、纳米碳酸钙或硫酸钡。
7.根据权利要求1所述的针对易挥发性酸的环保型气敏涂料，其特征在于，所述的助剂为流平剂、消泡剂、分散剂或防沉降剂。
8. 根据权利要求1所述的针对易挥发性酸的环保型气敏涂料，其特征在于，耐强酸树脂、特种变色剂A 、辅助变色组分、填料、助剂的质量比为 100：1-30：0.5-5：0-20：0-40。
9.根据权利要求1所述的针对易挥发性酸的环保型气敏涂料，其特征在于，耐强酸树脂、特种变色剂A 、辅助变色组分、填料、助剂的质量比为 100：5-20：10-20：15-30：1-5。
10.根据权利要求1所述的针对易挥发性酸的环保型气敏涂料，其特征在于，所述的针对易挥发性酸的环保型气敏涂料还包括25质量份的固化剂。
11.根据权利要求10所述的针对易挥发性酸的环保型气敏涂料，其特征在于，所述的固化剂为异氰酸酯固化剂或聚酰胺树脂。
12.根据权利要求1所述的针对易挥发性酸的环保型气敏涂料，其特征在于，化合物B对白炭黑处理过程如下：
将化合物B与白炭黑及溶剂进行共混，升温至溶剂进行回流，保持反应2-4小时，停止回流，随后减压蒸除溶剂，得到特种变色剂A。
13.权利要求1所述的针对易挥发性酸的环保型气敏涂料的制备方法，包括步骤如下：
按重量比将耐强酸树脂、特种变色剂A、辅助变色组分、填料、助剂、溶剂进行混合，搅拌分散均匀，然后研磨至细度小于40微米，得到涂料 A组分。
CN201911254671.XA 2019-12-08 2019-12-08 一种针对易挥发性酸的环保型气敏涂料及其制备方法 Active CN110922860B (zh)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN201911254671.XA CN110922860B (zh) 2019-12-08 2019-12-08 一种针对易挥发性酸的环保型气敏涂料及其制备方法
EP21194838.5A EP3960746A1 (en) 2019-12-08 2020-06-03 An environment-friendly gas-sensitive coating for volatile acids and the preparation method thereof
EP20178120.0A EP3831835A1 (en) 2019-12-08 2020-06-03 An environment-friendly gas-sensitive coating for volatile acids and the preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201911254671.XA CN110922860B (zh) 2019-12-08 2019-12-08 一种针对易挥发性酸的环保型气敏涂料及其制备方法

Publications (2)

Publication Number Publication Date
CN110922860A CN110922860A (zh) 2020-03-27
CN110922860B true CN110922860B (zh) 2021-07-20

Family

ID=69857908

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201911254671.XA Active CN110922860B (zh) 2019-12-08 2019-12-08 一种针对易挥发性酸的环保型气敏涂料及其制备方法

Country Status (2)

Country Link
EP (2) EP3960746A1 (zh)
CN (1) CN110922860B (zh)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115521727B (zh) * 2022-09-15 2023-03-31 北京中能航科科技有限公司 一种用于氨气泄漏检测的变色胶带及其制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1896081A (zh) * 2006-06-19 2007-01-17 浙江大学 一类含偶氮苯染料的硅氧烷先驱体及其合成方法
CN102977879A (zh) * 2012-12-03 2013-03-20 北京化工大学 一种通过共价键构筑的多酸基光致变色超分子自组装材料
CN103965480A (zh) * 2013-05-09 2014-08-06 江苏省农业科学院 一种超支化聚硅氧烷改性偶氮苯及其制备方法和应用
CN108707338A (zh) * 2018-05-17 2018-10-26 山东大学 一类荧光硅烷偶联剂及其制备方法与在室温硫化硅橡胶中的应用
CN109666376A (zh) * 2018-12-28 2019-04-23 陕西理工大学 一种可刺激响应变色功能涂料及其制备方法和应用

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4316041A (en) * 1980-02-19 1982-02-16 Union Carbide Corporation Liquid crystal silanes
JP4644818B2 (ja) * 2006-09-05 2011-03-09 国立大学法人群馬大学 色素増感太陽電池用色素及びこの色素を用いた光電変換素子並びに色素増感太陽電池
US9428652B2 (en) * 2007-06-01 2016-08-30 The Sherwin-Williams Company Color changing aqueous coatings
CN101855302B (zh) * 2007-08-23 2014-10-01 森馨颜色公司 自分散颜料及制造和使用该自分散颜料的方法
CN104607148A (zh) * 2015-01-12 2015-05-13 南京工业大学 一种智能光响应吸附剂、制备方法及其应用
CN106905833A (zh) 2017-04-05 2017-06-30 山西大学 一种具有警示功能的环保变色涂料及其制备方法
CN108485459A (zh) * 2018-03-20 2018-09-04 北华大学 一种环保型高固体分聚苯胺环氧防腐涂料及其制备方法
CN108530053B (zh) 2018-03-30 2021-03-30 华南理工大学 一种pH值敏感变色无机材料及其制备方法
CN110339827A (zh) * 2019-06-27 2019-10-18 延边大学 一种基于偶氮苯类光敏化合物修饰硅基的光敏色谱固定相

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1896081A (zh) * 2006-06-19 2007-01-17 浙江大学 一类含偶氮苯染料的硅氧烷先驱体及其合成方法
CN102977879A (zh) * 2012-12-03 2013-03-20 北京化工大学 一种通过共价键构筑的多酸基光致变色超分子自组装材料
CN103965480A (zh) * 2013-05-09 2014-08-06 江苏省农业科学院 一种超支化聚硅氧烷改性偶氮苯及其制备方法和应用
CN108707338A (zh) * 2018-05-17 2018-10-26 山东大学 一类荧光硅烷偶联剂及其制备方法与在室温硫化硅橡胶中的应用
CN109666376A (zh) * 2018-12-28 2019-04-23 陕西理工大学 一种可刺激响应变色功能涂料及其制备方法和应用

Also Published As

Publication number Publication date
EP3831835A1 (en) 2021-06-09
CN110922860A (zh) 2020-03-27
EP3960746A1 (en) 2022-03-02

Similar Documents

Publication Publication Date Title
CN105295645B (zh) 一种耐高温改性环氧漆及其制备方法和应用
CN112552772B (zh) 商用车底盘漆膜修补用水性环保自喷漆及其制备方法
CN110922860B (zh) 一种针对易挥发性酸的环保型气敏涂料及其制备方法
CN107083176A (zh) 一种聚氨酯镜面涂料及其制备方法
CN110669408B (zh) 一种纳米改性环氧树脂防腐涂料及其制备方法
CN111592614A (zh) 一种乙烯基改性氟碳树脂及其制备方法、耐腐蚀涂料及其制备方法和应用
CN104449391A (zh) 一种铁红防腐涂料及其制备方法
CN110804350B (zh) 一种遇酸变色警示涂料及其制备方法
CN110157333A (zh) 一种水性防腐涂料及其制备方法
CN109988493A (zh) 一种耐候性修补涂料组合物及其制备方法和用途
CN113637398A (zh) 一种底面合一型无溶剂聚天门冬氨酸酯重防腐涂料、制备方法及其应用
CN114716884A (zh) 一种大钢模板防锈涂料及制备方法
CN110819149B (zh) 一种纤维状稀土防锈颜料的制备方法
CN112358782A (zh) 一种高闪点丙烯酸防腐面漆及其制备方法
Wu et al. Self-repairing and anti-fouling performance of anticorrosive coating in marine environment
CN115232558B (zh) 一种自修复防水涂料及其制备方法
CN110003762A (zh) 一种高韧性强度阴极电泳漆涂料的制备方法
CN110746850A (zh) 一种新型硬化超耐磨地坪漆及其制备方法
CN113956442B (zh) 聚氨酯改性的非离子型水性胺类环氧树脂固化剂的制备方法
CN115477893A (zh) 一种水性醇酸防腐涂料的制备方法
CN106634513B (zh) 一种防腐涂料及其制备方法
CN114989707A (zh) 聚脲涂料
CN111808495A (zh) 一种耐冲击互穿网络防腐涂料
CN107141955B (zh) 水性彩板漆的研制方法
CN109762465B (zh) 一种污水管防腐防垢涂料及其制备方法

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
CB03 Change of inventor or designer information

Inventor after: Feng Shengyu

Inventor after: Wu Lianfeng

Inventor after: Wang Xianming

Inventor after: Lu Haifeng

Inventor before: Lu Haifeng

Inventor before: Wu Lianfeng

Inventor before: Wang Xianming

Inventor before: Feng Shengyu

CB03 Change of inventor or designer information
GR01 Patent grant
GR01 Patent grant