CN110527414A - Coating and preparation method thereof is unified in polyureas bottom surface to one kind at a slow speed - Google Patents
Coating and preparation method thereof is unified in polyureas bottom surface to one kind at a slow speed Download PDFInfo
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- CN110527414A CN110527414A CN201910841208.9A CN201910841208A CN110527414A CN 110527414 A CN110527414 A CN 110527414A CN 201910841208 A CN201910841208 A CN 201910841208A CN 110527414 A CN110527414 A CN 110527414A
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- 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
- C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
- C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
- C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
- C08G14/06—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols and monomers containing hydrogen attached to nitrogen
-
- 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
- C08G18/6415—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63 having nitrogen
- C08G18/6438—Polyimides or polyesterimides
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- 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
- C09D175/02—Polyureas
-
- 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
- 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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- 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
Abstract
Polyureas bottom surface unification coating and preparation method thereof, the bottom surface of the polyureas at a slow speed unification coating are formed one kind by base-material, curing agent and diluent mixture at a slow speed；The base-material is made of polyaspartic ester resin, front three etherified melamine amine-formaldehyde resins, cashew nut phenolic group phenolic aldehyde amine, pigment, filler, auxiliary agent and solvent.The invention also includes the preparation methods of the bottom surface of polyureas at a slow speed unification coating.Coating application working life >=4h of the present invention, 35~60min of surface drying time；This hair product is sprayed at metal or concrete substrate surface, it is fast and weather-proof with the excellent film of salt spray resistance to be capable of forming rate of drying.
Description
Technical field
The present invention relates to a kind of coating and preparation method thereof, and in particular to coating and its system are unified in polyureas bottom surface to one kind at a slow speed
Preparation Method.
Background technique
Polyaspartate is passed through by dialkyl maleate (or dialkyl fumarate) and aliphatic diamine
Michael addition reaction preparation, is changed into secondary amine for primary amine, reduces the reactivity of hydrogen atom and isocyano, while by
In steric effect, reaction speed is substantially reduced.
Initial response type diluent of the polyaspartate resin as solvent borne polyurethane coating, it can with contain hydroxyl
The polyester of base, acrylate copolymer mixing, reduce the VOC content in coating system.In the early 1990s in 20th century, two-component
Aliphatic polyurea Product industrialization.In traditional polyureas technology, gel time is from several seconds to a few minutes；And polyaspartate polyurea
Technology belongs to slow curing scope for common polyureas, and curing time is up to 120min.But in polyaspartate polyurea technology,
Construction working life after base-material cooperates with curing agent is still shorter, from a few minutes to dozens of minutes.It has been more than what working life cooperated
Material is not just available, therefore the application of working life short aspartate carbamide paint is extremely restricted.
The isocyanate component that polyaspartate polyurea technology uses is aliphatic isocyanates dimer or trimerization
Body.Thus weather resistance is excellent.The technology is mainly useful for the scumbling finishing coat that high glaze is paid special attention to excellent colour retention and applies
Workshop is closed, but salt spray resistance is still undesirable, can not be applied to bottom surface and be unified paint application.
CN104804633A discloses a kind of low-temperature quick-drying type acroleic acid polyurethane coating, and the coating is in mass ratio by A group
Divide and B component A:B=100:(20~27) composition；The composition components and mass percentage content of the component A are as follows: hydroxyl third
Olefin(e) acid resin 20~45%, amino resins 4~7%, modified polyaspartic ester 2~12%, pigment 4~10%, filler 8~
20%, dispersing agent 0.1~2%, defoaming agent 0.1~2%, levelling agent 0.1~2%, silane coupling agent 0.1~2%, PH regulator
0.1~2%, mixed solvent 15~25%；The B component is isophorone diisocyanate.With Hydroxylated acrylic resin, amino
Resin, modified polyaspartic ester and isophorone diisocyanate crosslinking form a film.But the invention does not describe amino resins
Concrete type and example, and contain small molecule alcohol solvent in the common amino resins that can be reacted with isocyanates, it can will be different
Cyanate curing agent sealing end, influences crosslink density.Furthermore Hydroxylated acrylic resin is introduced in this method, the shape in cross-linking process
Generating polyurethane segment, rather than pure carbamide paint, thus additional addition catalyst is needed to promote isocyanate groups and hydroxyl
Cross-linking reaction.
CN106243981A discloses a kind of high resistance to dust storm and corrodes wind-driven power generation blade coating and preparation method thereof, and the coating is by base
Material and curing agent mixture form, or further include diluent；The base-material has polyaspartic ester resin, polyurethane resin, face
Material, levelling agent, defoaming agent, anti-scratch auxiliary agent, catalysts and solvents；The curing agent has aliphatic isocyanates, polyether polyols
Pure and mild organometallic salt catalysts；The diluent has butyl acetate and high boiling solvent.The preparation method, including base-material
Preparation, the preparation of curing agent and the preparation of diluent finally by prepared base-material and curing agent, or are additionally added diluent and mix
Match,.Composition weather resistance is excellent, is suitable for finishing coat use, and salt spray resistance is not good enough, discomfort cooperation priming paint or bottom surface
Unify coating.
CN105593259A discloses a kind of coating composition, it includes: a) comprising the film-forming resin of secondary amine group, b) it is more
Isocyanate curing agent and c) solids of the polymer based on amino resins.The coating includes the film forming tree of secondary amine group
Rouge, polyisocyanate curing agent and the solids based on amino resins polymer, weather resistance is excellent, and salt spray resistance needs
It improves.
CN109266157A discloses a kind of preparation method of aqueous polyurea modified epoxy ester resin: the aqueous polyureas changes
Property epoxy ester resin be polyurea modified aliphatic epoxy ester prepolymer A formed with monomer mixture B graft copolymerization；The monomer is mixed
The mass ratio B/A for closing object B and prepolymer A is 0.35~0.95；The monomer mixture B by a variety of ethylene unsaturated monomers with
Initiator mixes；The prepolymer A is formed by aliphatic epoxy ester C and terminal isocyanate group polyureas D addition polymerization；It is described
The mass ratio D/C of the terminal isocyanate group polyureas D and aliphatic epoxy ester C is 0.02~0.20；The aqueous polyurea modified ring
Wherein diluent is propylene glycol methyl ether acetate to oxygen ester resin, and isocyanate curing agent can be sealed by still falling within small molecule alcohol solvent
End, influences film crosslink density.
CN105462484A discloses a kind of obtained primer-topcoat integrated anticorrosive painting modified based on polyaspartic ester
Material.Anticorrosive paint chemical component and mass percent be, polyaspartic ester 20%~35%, modified resin 10%~
18%, defoaming agent 0.2%~0.8%, levelling agent 0.3%~0.5%, UV absorbers 0.5%~1.5%, pigment 32%
~42%, filler 10%~25%, solvent 5%~10%, curing agent 20%~29%, delustering agent 1%~5%.It is documented
Coating film gloss is lower than 90%, can not be applied to the more demanding occasion of gloss.
Summary of the invention
The technical problem to be solved by the present invention is to overcome drawbacks described above of the existing technology, provide a kind of working life
Unify coating in the bottom surface of polyureas at a slow speed long, salt spray resistance is excellent, gloss is high.
The present invention provides one kind further the technical problem to be solved is that, overcome drawbacks described above of the existing technology
It is easy to operate, it is suitble to the preparation method of the bottom surface of the polyureas at a slow speed unification coating of industrialized production.
The technical solution adopted by the present invention to solve the technical problems is as follows: a kind of unification of polyureas bottom surface at a slow speed coating, by
Base-material, curing agent and diluent mixture form；The base-material is by polyaspartic ester resin, front three etherified melamine amine formaldehyde
Resin, cashew nut phenolic group phenolic aldehyde amine, pigment, filler, auxiliary agent and solvent composition.
Further, the polyaspartic ester resin by polymer A and polymer B 5~7:1 in mass ratio mixing and
At.
Further, the polymer A is by 3,3 ' dimethyl -4,4 '-diamino-dicyclohexyl methanes, two cashew nut of maleic acid
Phenolic ester, tertiary carbonic acid glycidyl ester are reacted according to molar ratio for 1.0: 1.75~1.95: 0.05~0.25；The polymer
B is Desmophen NH1420 or F420 resin.
Two cashew nut phenolic ester of maleic acid can effectively promote the salt spray resistance of film, and backbone improves poly-aspartic
Steric hindrance in acid ester resin near secondary amine structure is beneficial to extend the construction working life of coating；Tertiary carbonic acid glycidyl ester
Branched carbon chain structure can promote the weather resistance of smearing, moreover it is possible to extend the construction working life of coating, tertiary carbonic acid glycidyl
The epoxy group of ester plays the role of eliminating residual primary amine, is also conducive to extend the construction working life of coating.
Further, the solid of the front three etherified melamine amine-formaldehyde resins is divided into 80%, and solvent is aliphatic long-chain
Branching unit alcohol.The carbochain of the aliphatic long-chain branching unit alcohol is C16~C26；The aliphatic long-chain branching unit alcohol
There are two linear branches for tool, and branch point is in β-carbon potential or γ-carbon potential；Two branches of the aliphatic long-chain branching unit alcohol
The difference of carbon number is 2.The aliphatic long-chain branching unit alcohol is liquid under room temperature (20-25 DEG C).The aliphatic long-chain branch
The example for changing cell alcohol has 2- octyl dodecanol, 2- nonyl tridecanol.The triazine ring knot of front three etherified melamine amine-formaldehyde resins
Structure is conducive to be promoted the salt spray resistance of film；Aliphatic long-chain branching unit alcohol helps to improve coating film gloss.
Further, the aliphatic long-chain branching unit alcohol is 2- octyl dodecanol or 2- nonyl tridecanol.
Further, the cashew nut phenolic group phenolic aldehyde amine is the mixture of compound C and compound D, the compound C and chemical combination
The mass ratio of object D is 2.5~3.5: 1.Anacardol structural unit can be obviously improved the salt spray resistance of film, be conducive to film
The balance of weatherability and anti-corrosive properties.
Further, the compound C is anti-by anacardol, diethylenetriamine, paraformaldehyde and tertiary carbonic acid glycidyl ester
It should form；The compound D is reacted by anacardol, m-xylene diamine, butyraldehyde.M-xylene diamine helps to promote film
Salt spray resistance.
Further, the curing agent is aliphatic isocyanates tripolymer.
Further, it is that 1:1:1 is mixed that the diluent is propylene-glycol diacetate, butyl acetate, dimethylbenzene in mass ratio
It forms.
It is as follows that the present invention further solves technical solution used by its technical problem: a kind of unification of polyureas bottom surface at a slow speed painting
The preparation method of material, comprising the following steps:
(1) synthesis of polymer A: in the round-bottomed flask for being furnished with blender, heating mantle, nitrogen, dropping funel, thermocouple
In, 3,3 '-dimethyl -4 are added, 4 '-diamino-dicyclohexyl methanes instill two cashew nut phenolic ester of maleic acid at a temperature of control,
It is added dropwise and heats up, be then down to room temperature, stand；It heats up again, and tertiary carbonic acid glycidyl ester is added dropwise；Be added dropwise into
Row third time heats up,；
(2) synthesis of cashew nut phenolic group phenolic aldehyde amine C: in the three neck round bottom for being furnished with blender, condenser, thermocouple,
Anacardol and diethylenetriamine is added, stirs evenly and heats up；Then paraformaldehyde is added, heats up again after charging, into
Row reaction；Then the vacuum dehydration under stirring, cooling, with peristaltic pump be added dropwise tertiary carbonic acid glycidyl ester, be added dropwise into
Row heat preservation,；
(3) synthesis of cashew nut phenolic group phenolic aldehyde amine D: in the three neck round bottom for being furnished with blender, condenser, thermocouple,
Anacardol and m-xylene diamine is added, stirs evenly, is heated, butyraldehyde is added dropwise into mixture；Charging finishes heat preservation, carries out
It heats up, collects distillate in temperature-rise period；It keeps the temperature, heats up again again, it is cooling,；
(4) preparation of polyureas bottom surface unification coating at a slow speed: the poly- lucid asparagus that will be mixed by polymer A and polymer B
Obtained by ammonia acid ester resin, front three etherified melamine amine-formaldehyde resins, the cashew nut phenolic group phenolic aldehyde amine C obtained by step (2) and step (3)
Cashew nut phenolic group phenolic aldehyde amine that cashew nut phenolic group phenolic aldehyde amine D is mixed, barium sulfate, middle Huang, iron oxide red, silica, defoaming agent, levelling
Agent, dispersing agent, UV absorbers and solvent mixing, dispersion grinding is to get base-material；Base-material is mixed with curing agent,.
Further, in step (1), temperature≤50 DEG C of two cashew nut phenolic ester of the maleic acid instillation；The temperature of the heating
It is 55~60 DEG C；The time of the heating is 5~8h；The time of the standing >=12h；The temperature to heat up again be 60~
65 DEG C, the time≤30min that tertiary carbonic acid glycidyl is added dropwise；The temperature of the third time heating is 60~75 DEG C, third
The time of secondary heating >=2h；
Further, described to be warming up to 58~62 DEG C in step (2)；The temperature to heat up again is 96~100 DEG C, institute
State time >=2h of reaction；The vacuum dehydration is under conditions of vacuum degree is 0.085~0.095, temperature is 95~105 DEG C
It carries out, the time of the vacuum dehydration is 50~70min；The temperature of the cooling is 68~72 DEG C；It is described to be added dropwise with peristaltic pump
The speed of tertiary carbonic acid glycidyl ester is 2~3mL/min, and the temperature of the heat preservation is 78~82 DEG C, time >=2h of heat preservation；
Further, in step (3), the temperature heated is 47~50 DEG C, the time that butyraldehyde is added dropwise≤
60min；The temperature of the heat preservation is 47~54 DEG C, time >=60min of heat preservation；The temperature of the heating is 150~160 DEG C；
The temperature kept the temperature again is 160~165 DEG C, time >=20min of heat preservation；The temperature to heat up again is 165~170 DEG C；
The cooling time >=45min.
Compared with existing similar product, coating application working life of the present invention is longer, and surface drying time is shorter: construction working life >=
4h, surface drying time are 35~60min；This hair product is sprayed at metal or concrete substrate surface, is capable of forming rate of drying
The fast and weather-proof and excellent film of salt spray resistance.
Specific embodiment
Below with reference to embodiment, the invention will be further described.
Desmophen NH1420 used in embodiment is purchased from Covestro company, Germany, DESMODUR N3390
BA/SN curing agent (HDI trimer) is purchased from Covestro company, Germany；420 resin of F flies upward company purchased from Zhuhai.
Other chemical reagent used in embodiment are obtained by routine business approach unless otherwise specified.
Embodiment 1
The present embodiment at a slow speed consolidated by base-material and 35.1 mass parts DESMODUR N3390 BA/SN by polyureas bottom surface unification coating
Agent (HDI trimer, German Covestro company) mixture forms；The base-material is by 21.0 mass parts polyaspartic ester trees
Rouge (wherein polymer A, the 3.0 mass parts F420 resins of the preparation of 18.0 mass parts reference examples 1), 3.0 mass parts, three methyl-etherified three
Melamine-formaldehyde resin (80% solid point), 18.0 mass parts cashew nut phenolic group phenolic aldehyde amines (are prepared comprising 13.0 mass parts reference examples 2
Compound C, the preparation of 5.0 mass parts reference examples 3 compound D), 20.3 mass parts ultra-fine barium sulfates, in 23.0 mass parts it is yellow,
0.3 mass parts iron oxide red, 0.5 mass parts fumed silica, 0.3 mass parts defoaming agent, 0.4 mass parts levelling agent, 0.4 mass parts
Dispersing agent, 0.5 mass parts UV absorbers and 9.5 mass parts solvent mixtures form.
The present embodiment at a slow speed polyureas bottom surface unification coating preparation method, comprising the following steps:
(1) synthesis of polymer A: in the 2L round-bottomed flask for being furnished with blender, heating mantle, nitrogen, dropping funel, thermocouple
In, 3,3 ' dimethyl -4 238g, 4 '-diamino-dicyclohexyl methanes (1.0mol DMDC), by 1307.2g horse in 2h are added
Carry out sour two cashew nuts phenolic ester (1.9mol) to instill, temperature is no more than 50 DEG C.It is added dropwise, temperature is risen into 60 DEG C of maintenance 7h, cool down
12h is stood after to room temperature.65 DEG C are warming up to, 22.8g tertiary carbonic acid glycidyl ester (0.1mol) is added dropwise in 30min；It is added dropwise
75 DEG C of maintenance 2h are warming up to,.
(2) synthesis of cashew nut phenolic group phenolic aldehyde amine C: in the 1L three neck round bottom equipped with blender, condenser, thermocouple
In, 304g (1.0mol) anacardol and 145g (1.4mol) diethylenetriamine is added, stirs evenly and is warming up to 58~62 DEG C；It is slow
It is slow that 39g (1.3mol) paraformaldehyde is added, it is warming up to 96~100 DEG C after charging, reacts 2h；Then in stirring
In 95~105 DEG C of 50~70min of dehydration under 0.085~0.095 vacuum degree, 68~72 DEG C are cooled to, with the speed of 2.60mL/min
228g (1.0mol) tertiary carbonic acid glycidyl ester is added dropwise with peristaltic pump in degree, is added dropwise in 78~82 DEG C of heat preservation 2h,.
(3) synthesis of cashew nut phenolic group phenolic aldehyde amine D: in the 1L three neck round bottom equipped with blender, condenser, thermocouple
In, 304g (1.0mol) anacardol and 272g (2mol) m-xylene diamine is added, stirs evenly, purges flask contents with nitrogen
And it is heated to 48 DEG C；It is kept for 47~50 DEG C, butyraldehyde 144g (2mol) is added dropwise into mixture in 60min；Charging finishes
After 47~54 DEG C of heat preservation 60min, it is warming up to 160 DEG C；All distillates are collected in temperature-rise period；After 160 heat preservation 20min
170 DEG C are warming up to, flask contents are cooled down after 45min and is discharged,.
(4) preparation of polyureas bottom surface unification coating at a slow speed: by 21.0 mass parts polyaspartic ester resins (wherein 18.0
Mass parts reference example 1 prepare polymer A, 3.0 mass parts F420 resins), 3.0 mass parts front three etherified melamine amine formaldehyde trees
Rouge (80% solid point), 18.0 mass parts cashew nut phenolic group phenolic aldehyde amines (the compound C comprising the preparation of 13.0 mass parts reference examples 2,
The compound D of 5.0 mass parts reference examples 3 preparation), 20.3 mass parts ultra-fine barium sulfates, yellow, 0.3 mass parts in 23.0 mass parts
Iron oxide red, 0.5 mass parts fumed silica, 0.3 mass parts defoaming agent, 0.4 mass parts levelling agent, 0.4 mass parts dispersing agent,
0.5 mass parts UV absorbers and the mixing of 9.5 mass parts solvents, dispersion are ground to fineness less than 30 μm to get base ingredient.
Base-material and 35.1 mass parts DESMODUR N3390 BA/SN curing agent (HDI trimer, German Covestro company) are mixed,
.
Embodiment 2
The present embodiment at a slow speed consolidated by base-material and 34.8 mass parts DESMODUR N3390 BA/SN by polyureas bottom surface unification coating
Agent (HDI trimer, German Covestro company) mixture forms；The base-material is by 21.0 mass parts polyaspartic ester trees
Rouge (wherein 18.0 mass parts polymer A, 3.0 mass parts F420 resins), 3.0 mass parts front three etherified melamine amine-formaldehyde resins
(80% solid point), 18.0 mass parts cashew nut phenolic group phenolic aldehyde amines (include 13.5 mass part compound C, 4.5 mass part compounds
D), 20.3 mass parts ultra-fine barium sulfates, Huang in 23.0 mass parts, 0.3 mass parts iron oxide red, 0.5 mass parts fumed silica,
0.3 mass parts defoaming agent, 0.4 mass parts levelling agent, 0.4 mass parts dispersing agent, 0.5 mass parts UV absorbers and 9.5 matter
Amount part solvent mixture forms.
The present embodiment at a slow speed polyureas bottom surface unification coating preparation method, comprising the following steps: the synthesis of polymer A, waist
With embodiment 1, difference is only that for the synthesis of fruit phenolic group phenolic aldehyde amine C and the synthesis of cashew nut phenolic group phenolic aldehyde amine D:
The preparation of polyureas bottom surface unification coating at a slow speed: by 21.0 mass parts polyaspartic ester resin (wherein 18.0 matter
Measure part polymer A, 3.0 mass parts F420 resins), 3.0 mass parts front three etherified melamine amine-formaldehyde resins (80% solid point),
18.0 mass parts cashew nut phenolic group phenolic aldehyde amines (including 13.5 mass part compound C, 4.5 mass part compound D), 20.3 mass parts are super
Huang in thin barium sulfate, 23.0 mass parts, 0.3 mass parts iron oxide red, 0.5 mass parts fumed silica, 0.3 mass parts defoaming agent,
0.4 mass parts levelling agent, 0.4 mass parts dispersing agent, 0.5 mass parts UV absorbers and the mixing of 9.5 mass parts solvents, dispersion
Fineness is ground to less than 30 μm to get base ingredient.By base-material and 34.8 mass parts DESMODUR N3390 BA/SN curing agent
(HDI trimer, German Covestro company) mixing, prepares film.
Embodiment 3
The present embodiment at a slow speed consolidated by base-material and 34.6 mass parts DESMODUR N3390 BA/SN by polyureas bottom surface unification coating
Agent (HDI trimer, German Covestro company) mixture forms；The base-material is by 21.0 mass parts polyaspartic ester trees
Rouge (wherein 18.0 mass parts polymer A, 3.0 mass parts F420 resins), 3.0 mass parts front three etherified melamine amine-formaldehyde resins
(80% solid point), 18.0 mass parts cashew nut phenolic group phenolic aldehyde amines (include 13.9 mass part compound C, 4.1 mass part compounds
D), 20.3 mass parts ultra-fine barium sulfates, Huang in 23.0 mass parts, 0.3 mass parts iron oxide red, 0.5 mass parts fumed silica,
0.3 mass parts defoaming agent, 0.4 mass parts levelling agent, 0.4 mass parts dispersing agent, 0.5 mass parts UV absorbers and 9.5 matter
Amount part solvent mixture forms.
The present embodiment at a slow speed polyureas bottom surface unification coating preparation method, comprising the following steps: the synthesis of polymer A, waist
With embodiment 1, difference is only that for the synthesis of fruit phenolic group phenolic aldehyde amine C and the synthesis of cashew nut phenolic group phenolic aldehyde amine D:
The preparation of polyureas bottom surface unification coating at a slow speed: by 21.0 mass parts polyaspartic ester resin (wherein 18.0 matter
Measure part polymer A, 3.0 mass parts F420 resins), 3.0 mass parts front three etherified melamine amine-formaldehyde resins (80% solid point),
18.0 mass parts cashew nut phenolic group phenolic aldehyde amines (including 13.9 mass part compound C, 4.1 mass part compound D), 20.3 mass parts are super
Huang in thin barium sulfate, 23.0 mass parts, 0.3 mass parts iron oxide red, 0.5 mass parts fumed silica, 0.3 mass parts defoaming agent,
0.4 mass parts levelling agent, 0.4 mass parts dispersing agent, 0.5 mass parts UV absorbers and the mixing of 9.5 mass parts solvents, dispersion
Fineness is ground to less than 30 μm to get base ingredient.By base-material and 34.6 mass parts DESMODUR N3390 BA/SN curing agent
(HDI trimer, German Covestro company) mixing, prepares film.
Comparative example 1
By 21.0 mass parts polyaspartic ester resin (wherein 18.0 mass parts Desmophen NH1520,3.0 mass
Part F420 resin), 3.0 mass parts front three etherified melamine amine-formaldehyde resins (80% solid point), 18.0 mass parts cashew nut phenolic group
Phenolic aldehyde amine (including 13.5 mass part compound C, 4.5 mass part compound D), 20.3 mass parts ultra-fine barium sulfates, 23.0 mass
Part in Huang, 0.3 mass parts iron oxide red, 0.5 mass parts fumed silica, 0.3 mass parts defoaming agent, 0.4 mass parts levelling agent,
0.4 mass parts dispersing agent, 0.5 mass parts UV absorbers and the mixing of 9.5 mass parts solvents, dispersion are ground to fineness less than 30
μm to get base ingredient.By base-material and 43.6 mass parts Desmodur N3390 BA/SN curing agent (HDI trimer, Germany
Covestro company) mixing, prepare film.
Comparative example 2
By 21.0 mass parts polyaspartic ester resins (wherein 18.0 mass parts polymer A, 3.0 mass parts F420 trees
Rouge), 2.8 mass parts Resimene 717 (84% solid point, INEOS company), 18.0 mass parts cashew nut phenolic group phenolic aldehyde amines (include
13.5 mass part compound C, 4.5 mass part compound D), 20.3 mass parts ultra-fine barium sulfates, yellow, 0.3 matter in 23.0 mass parts
Measure part iron oxide red, 0.5 mass parts fumed silica, 0.3 mass parts defoaming agent, 0.4 mass parts levelling agent, the dispersion of 0.4 mass parts
Agent, 0.5 mass parts UV absorbers and the mixing of 9.5 mass parts solvents, dispersion are ground to fineness less than 30 μm to get base-material group
Point.Base-material and 35.2 mass parts DESMODUR N3390 BA/SN curing agent (HDI trimer, German Covestro company) is mixed
It closes, prepares film.
Comparative example 3
By 21.0 mass parts polyaspartic ester resins (wherein 18.0 mass parts polymer A, 3.0 mass parts F420 trees
Rouge), 3.0 mass parts front three etherified melamine amine-formaldehyde resins (80% solid point), 18.0 mass parts cashew nut phenolic group phenolic aldehyde amine NX-
2015 (Ka Delai), 20.3 mass parts ultra-fine barium sulfates, Huang, 0.3 mass parts iron oxide red, 0.5 mass parts gas phase in 23.0 mass parts
Silica, 0.3 mass parts defoaming agent, 0.4 mass parts levelling agent, 0.4 mass parts dispersing agent, 0.5 mass parts UV Absorption
Agent and the mixing of 9.5 mass parts solvents, dispersion are ground to fineness less than 30 μm to get base ingredient.By base-material and 19.6 mass parts
DESMODUR N3390 BA/SN curing agent (HDI trimer, German Covestro company) mixing, prepares film.
The detection of the coating and film of embodiment and comparative example:
Comparative example 1 shows that two cashew nut phenolic ester of maleic acid can effectively extend the construction working life of coating and promote coating film gloss；
Comparative example 2 shows that the low molecule alcohol solvent of common amino resins reduces film crosslink density, and gloss is made to reduce, is weather-proof
Performance decline, and aliphatic long-chain branching unit alcohol is then obviously improved gloss；Comparative example 3 shows unmodified anacardol
The remaining primary amine of phenolic aldehyde amine has been obviously shortened coating applicable period；Examples 1 to 3 shows the construction of carbamide paint at a slow speed of the invention
Working life is up to 4h, and for surface drying time in 45~55min range, gloss (60 °) is higher (being greater than 90%), and film is weather-proof and salt spray resistance
Performance is excellent, and the dosage for increasing compound D can effectively shorten film surface drying time, promoted coating film gloss.
Claims (10)
1. coating is unified in a kind of polyureas bottom surface at a slow speed, it is characterised in that: formed by base-material, curing agent and diluent mixture；It is described
Base-material by polyaspartic ester resin, front three etherified melamine amine-formaldehyde resins, cashew nut phenolic group phenolic aldehyde amine, pigment, filler, help
Agent and solvent composition.
2. coating is unified in the bottom surface of polyureas at a slow speed according to claim 1, it is characterised in that: the polyaspartic ester tree
Rouge is mixed by polymer A and polymer B 5~7:1 in mass ratio；
The polymer A is by 3,3 ' dimethyl -4,4 '-diamino-dicyclohexyl methane, two cashew nut phenolic ester of maleic acid, versatic acid
Ethylene oxidic ester is reacted according to molar ratio for 1.0: 1.75~1.95: 0.05~0.25；
The polymer B is Desmophen NH1420 or F420 resin.
3. coating is unified in the bottom surface of polyureas at a slow speed according to claim 1 or 2, it is characterised in that: the three methyl-etherifieds trimerization
The solid of cyanamide formaldehyde resin is divided into 80%, and solvent is aliphatic long-chain branching unit alcohol.
4. coating is unified in the bottom surface of polyureas at a slow speed according to claim 3, it is characterised in that: the aliphatic long-chain branching list
First alcohol is 2- octyl dodecanol or 2- nonyl tridecanol.
5. coating is unified in polyureas bottom surface at a slow speed according to one of claim 2~4, it is characterised in that: the cashew nut phenolic group
Phenolic aldehyde amine is the mixture of compound C and compound D, and the mass ratio of the compound C and compound D is 2.5~3.5: 1；
The compound C is reacted by anacardol, diethylenetriamine, paraformaldehyde and tertiary carbonic acid glycidyl ester；
The compound D is reacted by anacardol, m-xylene diamine, butyraldehyde.
6. coating is unified in polyureas bottom surface at a slow speed described according to claim 1~one of 5, it is characterised in that: the curing agent is
Aliphatic isocyanates tripolymer；The diluent is propylene-glycol diacetate, butyl acetate, dimethylbenzene are 1:1 in mass ratio:
1 mixture forms.
7. a kind of preparation method of the unification of polyureas bottom surface at a slow speed coating as claimed in claim 5, it is characterised in that: including following
Step:
(1) synthesis of polymer A: in the round-bottomed flask for being furnished with blender, heating mantle, nitrogen, dropping funel, thermocouple, add
Enter 3,3 '-dimethyl -4, two cashew nut phenolic ester of maleic acid is instilled at a temperature of control, dripped by 4 '-diamino-dicyclohexyl methanes
Bi Jinhang heating, is then down to room temperature, stands；It heats up again, and tertiary carbonic acid glycidyl ester is added dropwise；Carry out third is added dropwise
Secondary heating,;
(2) it the synthesis of cashew nut phenolic group phenolic aldehyde amine C: in the three neck round bottom for being furnished with blender, condenser, thermocouple, is added
Anacardol and diethylenetriamine are stirred evenly and are heated up；Then paraformaldehyde is added, heats up again after charging, carries out anti-
It answers;Then the vacuum dehydration under stirring, cooling are added dropwise tertiary carbonic acid glycidyl ester with peristaltic pump, are added dropwise and are protected
Temperature,；
(3) it the synthesis of cashew nut phenolic group phenolic aldehyde amine D: in the three neck round bottom for being furnished with blender, condenser, thermocouple, is added
Anacardol and m-xylene diamine, stir evenly, and are heated, and butyraldehyde is added dropwise into mixture；Charging finishes heat preservation, is risen
Temperature collects distillate in temperature-rise period；It keeps the temperature, heats up again again, it is cooling,；
(4) preparation of polyureas bottom surface unification coating at a slow speed: the poly-aspartic-acid that will be mixed by polymer A and polymer B
Cashew nut obtained by ester resin, front three etherified melamine amine-formaldehyde resins, the cashew nut phenolic group phenolic aldehyde amine C obtained by step (2) and step (3)
Cashew nut phenolic group phenolic aldehyde amine that phenolic group phenolic aldehyde amine D is mixed, barium sulfate, middle Huang, iron oxide red, silica, defoaming agent, levelling agent,
Dispersing agent, UV absorbers and solvent mixing, dispersion grinding is to get base-material；Base-material is mixed with curing agent,.
8. the preparation method of unification coating in the bottom surface of polyureas at a slow speed according to claim 7, it is characterised in that: in step (1),
Temperature≤50 DEG C that the two cashew nut phenolic ester of maleic acid instills；The temperature of the heating is 55~60 DEG C；The time of the heating
For 5~8h；The time of the standing >=12h；The temperature to heat up again is 60~65 DEG C, and the dropwise addition versatic acid shrinks sweet
Time≤30min of oil；The temperature of the third time heating is 60~75 DEG C, time >=2h of third time heating.
9. the preparation method of unification coating in the bottom surface of polyureas at a slow speed according to claim 7 or 8, it is characterised in that: step (2)
In, it is described to be warming up to 58~62 DEG C；The temperature to heat up again is 96~100 DEG C, time >=2h of the reaction；It is described true
Sky dehydration is carries out under conditions of vacuum degree is 0.085~0.095, temperature is 95~105 DEG C, the time of the vacuum dehydration
For 50~70 min；The temperature of the cooling is 68~72 DEG C；The speed that tertiary carbonic acid glycidyl ester is added dropwise with peristaltic pump
For 2~3mL/ min, the temperature of the heat preservation is 78~82 DEG C, time >=2h of heat preservation.
10. the preparation method of coating is unified in polyureas bottom surface at a slow speed according to one of claim 7~9, it is characterised in that: step
Suddenly in (3), the temperature heated is 47~50 DEG C, the time≤60min that butyraldehyde is added dropwise；The temperature of the heat preservation
It is 47~54 DEG C, time >=60min of heat preservation；The temperature of the heating is 150~160 DEG C;The temperature kept the temperature again be 160~
165 DEG C, time >=20min of heat preservation；The temperature to heat up again is 165~170 DEG C；The cooling time >=45min.
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