CN106398464A - Biomass oil modified epoxy resin anticorrosive coating and preparation method thereof - Google Patents
Biomass oil modified epoxy resin anticorrosive coating and preparation method thereof Download PDFInfo
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- CN106398464A CN106398464A CN201610786147.7A CN201610786147A CN106398464A CN 106398464 A CN106398464 A CN 106398464A CN 201610786147 A CN201610786147 A CN 201610786147A CN 106398464 A CN106398464 A CN 106398464A
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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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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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
- 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
- C08G59/14—Polycondensates modified by chemical after-treatment
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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
- 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
- C08G59/50—Amines
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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
- 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
- C08G59/50—Amines
- C08G59/5006—Amines aliphatic
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- 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
- C08K3/08—Metals
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- 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
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- 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
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- 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
- C08K3/346—Clay
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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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
- C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
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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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
- C09D5/10—Anti-corrosive paints containing metal dust
- C09D5/106—Anti-corrosive paints containing metal dust containing Zn
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B1/00—Production of fats or fatty oils from raw materials
- C11B1/10—Production of fats or fatty oils from raw materials by extracting
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B3/00—Refining fats or fatty oils
- C11B3/12—Refining fats or fatty oils by distillation
-
- 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
- C08K3/08—Metals
- C08K2003/0893—Zinc
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- 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
Abstract
The invention discloses a biomass oil modified epoxy resin anticorrosive coating and a preparation method thereof. The anticorrosive coating includes a coating component and a curing component; the coating component comprises the following raw materials by the mass percentage: 30-43% of biomass oil modified epoxy resin, 5-15% of an organic solvent, 0.1-0.5% of a coloring pigment, 35-58% of an extender pigment, 2-8% of an anticorrosive pigment, 0.3-2.8% of a thixotropic agent, 0.1-0.8% of a dispersing agent and 0.1-0.9% of a defoaming agent, wherein the sum of the mass percentages of all the raw materials is 100%. The anticorrosive coating has excellent toughness, corrosion resistance, impact resistance, cracking resistance and weather resistance; the preparation method is simple, stable in process, and mild in reaction conditions, can make full use of biomass materials, saves energy, is environmentally friendly, increases the added utilization value of biomass energy, and reduces the production cost.
Description
Technical field
The invention belongs to coating manufactures field and in particular to a kind of bio-oil modified epoxy anticorrosive paint and its system
Preparation Method.
Background technology
Anticorrosive paint is generally divided into conventional anticorrosive paint and anticorrosive paint, is requisite a kind of painting in paint
Material.Conventional anticorrosive paint is under general condition, and metal etc. is played with etch-proof effect, the longevity that protection non-ferrous metal uses
Life；For anticorrosive paint refers to relatively conventional anticorrosive paint, can apply in relatively harsh corrosive environment, and have and can reach
The one class anticorrosive paint of protection period longer than conventional anticorrosive paint.
The usual products of anticorrosive paint have epoxy coating, ceramic filler coating, epoxy novolac coating, macromolecule to be combined
Material and anti-corrosion polyurethane coating etc..In these coating systems, epoxy coating is applied to protective conduit from abrasion
And external corrosion.Epoxy resin is to refer to the organic compound containing two or more epoxide groups in molecule, has
The adhesive property of excellent physical and mechanical properties, electrical insulation capability and various material, and have flexibly special using technique
Point.These functions and feature are not available for other thermosetting plasticses, therefore it can make coating, composite, casting material,
Adhesive, moulding material and injecting forming material, are all widely used in the every field of national economy.Epoxy resin
There is following general character：1st, chemical-resistant is excellent, especially alkali resistance；2nd, paint film adhesion is strong, particularly to metal；3rd, have
Preferably heat resistance and electrical insulating property；4th, paint film colour retention is preferable.But the weatherability of epoxy coating is poor, and fragility is larger,
Cracking resistance shock resistance is poor, and easily efflorescence loss of gloss owes plentiful to paint film again out of doors, should not make outdoor coating and high-decoration applies
Material is used.Therefore, it is badly in need of finding a kind of toughness, antiseptic property, shock resistance anti-cracking performance and the excellent asphalt mixtures modified by epoxy resin of weather resistance
Fat anticorrosive paint.
Content of the invention
It is an object of the invention to：For the toughness of above-mentioned anti-corrosive paint of epoxy resin, antiseptic property, shock resistance cracking resistance
Performance and the problem of weather resistance difference, the present invention provides a kind of bio-oil modified epoxy anticorrosive paint and its preparation side
Method.
The technical solution used in the present invention is as follows：
A kind of bio-oil modified epoxy anticorrosive paint, including coating composition and curing component, described coating composition
Raw material including following mass percent：30～43% bio-oil modified epoxies, 5～15% organic solvents, 0.1～
0.5% coloring pigment, 35～58% extender pigments, 2～8% corrosion-inhibitive pigments, 0.3～2.8% thixotropic agent, 0.1～0.8% point
Powder and 0.1～0.9% defoamer, the mass percent sum of each raw material is 100%.This coating composition is changed using bio-oil
Property epoxy resin as raw material, because epoxy resin is modified through bio-oil, its toughness, antiseptic property and weather resistance
It is improved, therefore, anticorrosive paint be can be used as by coating prepared by bio-oil modified epoxy.
The preparation method of described bio-oil modified epoxy, its step is：By 50～100 parts of epoxy resin, dilution
Agent A20～80 part and 20～100 parts of bio-oil sequentially add to reactor, start reactor stirring, are to slowly warm up to 50
～65 DEG C, add 0.2～1.5 part of base catalyst, be heated to 60～75 DEG C and be incubated 0.5～2.0h, add metallic salt to urge
0.1～0.8 part of agent, flows back and is incubated 0.5～2.0h after being heated to 75～85 DEG C, cooling obtains bio-oil modified epoxy tree
Fat.The preparation method of this bio-oil modified epoxy, is modified to epoxy resin by chemical method, by bio-oil
The groups such as the phenolic hydroxyl group that contains in strand, carboxyl are incorporated in the molecular structure of epoxy resin.Bio-oil have good toughness,
The excellent specific property such as weather resistance is good, antiseptic property is good, is modified to epoxy resin using bio-oil, can improve epoxy resin
Toughness, weather resistance and shock resistance anti-cracking performance etc..
The preparation method of described bio-oil is as follows：
(1) extract：By weight, the life 20～100 parts of commercially available lignin, cellulose and hemicellulose being cracked and coming
Material crude oil is added in container, adds 20～80 parts of stirrings of distilled water, and is warming up to 40～50 DEG C, is incubated 20～60min, quiet
Put and be layered and remove supernatant liquor, add 10～50 parts of stirrings of distilled water, and be warming up to 60～80 DEG C, be incubated 20～60min, quiet
Put and be layered and remove supernatant liquor；
(2) distill：Parts by weight, the bio-oil that (1) is extracted is heated to 80～105 DEG C, vacuum distillation, removes water
Point, add 10～50 parts of diluent A to obtain bio-oil.
Described epoxy resin includes bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, phenolic aldehyde
One of type epoxy resin and resorcinol type epoxy.
Described base catalyst is one of potassium hydroxide, NaOH, calcium acetate, barium hydroxide and magnesium carboxylates, gold
Genus saline catalyst is one of ferric trichloride, boron chloride and aluminium isopropoxide, diluent A be selected from ethanol, n-butanol,
One or more of butyl acetate, ethyl acetate, oxolane, ethylene glycol and glycerine.
Described curing component includes the raw material of following mass percent：70～90% amine hardeners, 1～2.5% epoxy promote
Enter agent and 9～21% organic solvents, the mass percent of each raw material is 100%, curing component is used for making coating composition solidify.
Described organic solvent include one of acetone, n-butanol, butyl acetate, toluene, dimethylbenzene and oxolane or
Multiple, coloring pigment includes one or more of titanium dioxide, iron oxide red, iron oxide yellow, carbon black and chrome green, extender pigment bag
Include one or more of talcum powder, mica powder, aluminium hydroxide and bentonite, corrosion-inhibitive pigments include zinc powder or aluminium powder or zinc powder
With the mixture of aluminium powder, thixotropic agent includes one or more of organobentonite, kaolin and silica, and dispersant is profit
Hygroscopic water powder, defoamer is organic silicon defoamer.
Described amine hardener includes phenol aldehyde modified amine T31,650 polyamide, 651 polyamide, 701 phenol aldehyde modified amine and 702
One or more of phenol aldehyde modified amine, epoxy accelerator include one of triethanolamine, dimethylaniline and DMP-30 or
Multiple.
A kind of preparation method of bio-oil modified epoxy anticorrosive paint, comprises the following steps：
(1) described bio-oil modified epoxy is mixed with 3～10% organic solvents, add coloring pigment, physique
Pigment, corrosion-inhibitive pigments, thixotropic agent, dispersant and defoamer, the rotating speed pressing 1500～3000 turns/min at 45～55 DEG C is high
Speed dispersion 30min, adds 2～5% organic solvents, stirs, and curing obtained coating composition after 1 day；
(2) amine hardener, epoxy accelerator and organic solvent are mixed, stir at normal temperatures, obtain curing component；
(3) prepare anticorrosive paint：Coating composition and curing component are pressed (10～17):1 mass ratio mixing, adds dilution
Agent B stirs, and obtains bio-oil modified epoxy anticorrosive paint after curing 15min.
Described diluent B group by mass percentage is divided into 50～80% dimethylbenzene and 20～50% isobutanols, each component
Mass percent sum be 100%.
In sum, due to employing technique scheme, the invention has the beneficial effects as follows：
1. provide a kind of bio-oil modified epoxy anticorrosive paint, this anticorrosive paint has excellent toughness, prevents
Rotten performance, shock resistance anti-cracking performance and weather resistance；
2. provide a kind of preparation method of bio-oil modified epoxy anticorrosive paint, the method is simple, and technique is steady
Fixed, reaction condition is gentle；
3. using bio-oil, epoxy resin is modified, biological material, energy-conserving and environment-protective can be made full use of, improve life
The additional value of the material energy；
4. the raw material adopting are easy to get, and cheap, it is possible to decrease production cost.
Specific embodiment
All features disclosed in this specification, in addition to mutually exclusive feature and/or step, all can be with any
Mode combines.
A kind of bio-oil modified epoxy anticorrosive paint, including coating composition and curing component, described coating composition
Raw material including following mass percent：30～43% bio-oil modified epoxies, 5～15% organic solvents, 0.1～
0.5% coloring pigment, 35～58% extender pigments, 2～8% corrosion-inhibitive pigments, 0.3～2.8% thixotropic agent, 0.1～0.8% point
Powder and 0.1～0.9% defoamer, the mass percent sum of each raw material is 100%.
Preferably, the preparation method of bio-oil modified epoxy, its step is：By 50～100 parts of epoxy resin, dilute
Release 20～80 parts of agent A and 20～100 parts of bio-oil sequentially adds to reactor, start reactor stirring, be to slowly warm up to
50～65 DEG C, add 0.2～1.5 part of base catalyst, be heated to 60～75 DEG C and be incubated 0.5～2.0h, add metallic salt
0.1～0.8 part of catalyst, flows back and is incubated 0.5～2.0h after being heated to 75～85 DEG C, cooling obtains bio-oil modified epoxy
Resin.
Preferably, the preparation method of bio-oil is as follows：
(1) extract：By weight, the life 20～100 parts of commercially available lignin, cellulose and hemicellulose being cracked and coming
Material crude oil is added in container, adds 20～80 parts of stirrings of distilled water, and is warming up to 40～50 DEG C, is incubated 20～60min, quiet
Put and be layered and remove supernatant liquor, add 10～50 parts of stirrings of distilled water, and be warming up to 60～80 DEG C, be incubated 20～60min, quiet
Put and be layered and remove supernatant liquor；
(2) distill：By weight, the bio-oil (1) being extracted is heated to 80～105 DEG C, vacuum distillation, removes water
Point, add 10～50 parts of diluent A to obtain bio-oil.
Preferably, epoxy resin includes bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, phenol
One of aldehyde type epoxy resin and resorcinol type epoxy.
Preferably, base catalyst is one of potassium hydroxide, NaOH, calcium acetate, barium hydroxide and magnesium carboxylates,
Metallic salt catalyst is one of ferric trichloride, boron chloride and aluminium isopropoxide, and diluent A is selected from ethanol, positive fourth
One or more of alcohol, butyl acetate, ethyl acetate, oxolane, ethylene glycol and glycerine.
Preferably, curing component includes the raw material of following mass percent：70～90% amine hardeners, 1～2.5% epoxy
Accelerator and 9～21% organic solvents, the mass percent of each raw material is 100%, and curing component is used for making coating composition solidify.
Preferably, organic solvent includes one of acetone, n-butanol, butyl acetate, toluene, dimethylbenzene and oxolane
Or multiple, coloring pigment includes one or more of titanium dioxide, iron oxide red, iron oxide yellow, carbon black and chrome green, extender pigment
Including one or more of talcum powder, mica powder, aluminium hydroxide and bentonite, corrosion-inhibitive pigments include zinc powder or aluminium powder or zinc
Powder and the mixture of aluminium powder, thixotropic agent includes one or more of organobentonite, kaolin and silica, and dispersant is
Wetting dispersing agent, defoamer is organic silicon defoamer.
Preferably, amine hardener include phenol aldehyde modified amine T31,650 polyamide, 651 polyamide, 701 phenol aldehyde modified amine and
One or more of 702 phenol aldehyde modified amine, epoxy accelerator includes one of triethanolamine, dimethylaniline and DMP-30
Or it is multiple.
A kind of preparation method of bio-oil modified epoxy anticorrosive paint, comprises the following steps：
(1) described bio-oil modified epoxy is mixed with 3～10% organic solvents, add coloring pigment, physique
Pigment, corrosion-inhibitive pigments, thixotropic agent, dispersant and defoamer, the rotating speed pressing 1500～3000 turns/min at 45～55 DEG C is high
Speed dispersion 30min, adds 2～5% organic solvents, stirs, and curing obtained coating composition after 1 day；
(2) amine hardener, epoxy accelerator and organic solvent are mixed, stir at normal temperatures, obtain curing component；
(3) prepare anticorrosive paint：Coating composition and curing component are pressed (10～17):1 mass ratio mixing, adds dilution
Agent B stirs, and obtains bio-oil modified epoxy anticorrosive paint after curing 15min.
Preferably, diluent B group by mass percentage is divided into 50～80% dimethylbenzene and 20～50% isobutanols, each group
The mass percent sum divided is 100%.
Embodiment 1
The preparation method of bio-oil is as follows：
(1) extract：100 parts of the biomass crude oil that the cracking of commercially available lignin, cellulose and hemicellulose is come is added to
In there-necked flask, add 80 parts of stirrings of distilled water, and be warming up to 50 DEG C, be incubated 60min, stratification 30min simultaneously removes upper strata
Clear liquid, adds 50 parts of stirrings of distilled water, and is warming up to 80 DEG C, be incubated 60min, stratification 30min simultaneously removes supernatant liquor；
(2) distill：By extraction after bio-oil be heated to 105 DEG C, vacuum distillation, control vacuum be -0.095～-
0.09MPa, removes moisture, obtains the liquid bio matter oil of toughness, adds 50 parts of ethanol to obtain bio-oil.Gained living beings
In oil, the mass percent of solid content is 64.2%, and the average molecular mass Mn of bio-oil is 400～3000, preferably mean molecule
Amount Mn is 500～1000 bio-oil.
Embodiment 2
The preparation method of bio-oil is as follows：
(1) extract：60 parts of the biomass crude oil that the cracking of commercially available lignin, cellulose and hemicellulose is come is added to three
In mouthful flask, add 50 parts of stirrings of distilled water, and be warming up to 45 DEG C, be incubated 40min, stratification 30min to remove upper strata clear
Liquid, adds 30 parts of stirrings of distilled water, and is warming up to 70 DEG C, be incubated 40min, stratification 30min simultaneously removes supernatant liquor；
(2) distill：By extraction after bio-oil be heated to 100 DEG C, vacuum distillation, control vacuum be -0.095～-
0.09MPa, removes moisture, obtains the liquid bio matter oil of toughness, adds 30 parts of ethyl acetate to obtain bio-oil.Gained is given birth to
In material oil, the mass percent of solid content is 64.7%, and the average molecular mass Mn of bio-oil is 400～3000, preferably averagely
Molecular weight Mn is 500～1000 bio-oil.
Embodiment 3
The preparation method of bio-oil is as follows：
(1) extract：30 parts of the biomass crude oil that the cracking of commercially available lignin, cellulose and hemicellulose is come is added to three
In mouthful flask, add 20 parts of stirrings of distilled water, and be warming up to 45 DEG C, be incubated 30min, stratification 30min to remove upper strata clear
Liquid, adds 10 parts of stirrings of distilled water, and is warming up to 65 DEG C, be incubated 30min, stratification 30min simultaneously removes supernatant liquor；
(2) distill：By extraction after bio-oil be heated to 95 DEG C, vacuum distillation, control vacuum be -0.095～-
0.09MPa, removes moisture, obtains the liquid bio matter oil of toughness, adds 15 parts of oxolane to obtain bio-oil.Gained is given birth to
In material oil, the mass percent of solid content is 61.3%, and the average molecular mass Mn of bio-oil is 400～3000, preferably averagely
Molecular weight Mn is 500～1000 bio-oil.
Embodiment 4
Based on embodiment 1, the preparation method of bio-oil modified epoxy is：By bisphenol A type epoxy resin E-51 (ring
Oxygen value 0.516) 60 parts, 30 parts of ethanol and 40 parts of described bio-oil sequentially add to reactor, start reactor stirring
30min, is to slowly warm up to 55 DEG C, adds 0.5 part of potassium hydroxide, is heated to 65 DEG C and is incubated 1.5h, adds ferric trichloride 0.3
Part, flow back after being heated to 75 DEG C and be incubated, start to measure epoxide number after insulation 20min, when epoxide number is 0.20～0.25
Stop reaction, be cooled to 35 DEG C at once and obtain bio-oil modified epoxy.
Embodiment 5
Based on embodiment 2, the preparation method of bio-oil modified epoxy is：By bisphenol f type epoxy resin (epoxide number
0.466) 80 parts, 50 parts of ethyl acetate and 60 parts of described bio-oil sequentially add to reactor, start reactor stirring
30min, is to slowly warm up to 60 DEG C, adds 0.9 part of calcium acetate, is heated to 70 DEG C and is incubated 2.0h, adds aluminium isopropoxide 0.5
Part, flow back after being heated to 80 DEG C and be incubated, start to measure epoxide number after insulation 20min, when epoxide number is 0.20～0.25
Stop reaction, be cooled to 35 DEG C at once and obtain bio-oil modified epoxy.
Embodiment 6
Based on embodiment 3, the preparation method of bio-oil modified epoxy is：By phenol aldehyde type epoxy resin F44 (epoxy
Value 0.457) 100 parts, 60 parts of oxolane and 80 parts of described bio-oil sequentially add to reactor, start reactor stirring
30min, is to slowly warm up to 65 DEG C, adds 1.3 parts of magnesium carboxylates, is heated to 75 DEG C and is incubated 1.5h, adds 0.6 part of boron chloride,
Flow back after being heated to 85 DEG C and be incubated, start to measure epoxide number after insulation 20min, stop when epoxide number is 0.20～0.25
Reaction, is cooled to 35 DEG C at once and obtains bio-oil modified epoxy.
Embodiment 7
Based on above-described embodiment 1 and embodiment 4, by mass percentage, by bio-oil modified epoxy described in 43%
Mix with 8% n-butanol, add 0.5% titanium dioxide, 37% talcum powder, 4% zinc powder, 2.5% kaolin, 0.4% wetting and dispersing
Agent and 0.6% organic silicon defoamer, disperse 30min at a high speed with the rotating speed of 1500 turns/min at 45 DEG C, add 4% acetone,
Stir, curing obtained coating composition after 1 day；By mass percentage, by 90% phenol aldehyde modified amine T31,1% triethanolamine and
9% butyl acetate mixing, stirs at normal temperatures, obtains curing component；By mass percentage, by 50% dimethylbenzene and 50%
Isobutanol stirs, and obtains diluent B, then by coating composition and curing component in mass ratio for 10:1 mixing, adds
Appropriate diluent B stirs, and obtains bio-oil modified epoxy anticorrosive paint after curing 15min.
Embodiment 8
Based on above-described embodiment 2 and embodiment 5, by mass percentage, by bio-oil modified epoxy described in 36%
Mix with 9% butyl acetate, add 0.3% iron oxide red, 44% mica powder, 3% aluminium powder, 1.7% organobentonite, 0.5%
Wetting dispersing agent and 0.5% organic silicon defoamer, disperse 30min at a high speed with the rotating speed of 3000 turns/min at 50 DEG C, add
5% acetone, stirs, and curing obtained coating composition after 1 day；By mass percentage, by 80%702 phenol aldehyde modified amine, 2% 2
Methylaniline and the mixing of 18% n-butanol, stir at normal temperatures, obtain curing component；By mass percentage, by 60% 2
Toluene and 40% isobutanol stir, and obtain diluent B, then by coating composition and curing component in mass ratio for 14:1 mixes
Close, add appropriate diluent B and stir, after curing 15min, obtain bio-oil modified epoxy anticorrosive paint.
Embodiment 9
Based on above-described embodiment 3 and embodiment 6, by mass percentage, by bio-oil modified epoxy described in 30%
Mix with 10% acetone, add 0.4% chrome green, 50% aluminium hydroxide, 3.6% zinc powder, 1.5% silica, 0.7% wetting point
Powder and 0.8% organic silicon defoamer, disperse 30min at a high speed with the rotating speed of 2000 turns/min at 50 DEG C, add 3% tetrahydrochysene
Furans, stirs, and curing obtained coating composition after 1 day；By mass percentage, by 77%650 polyamide, 2%DMP-30 and
21% n-butanol mixing, stirs at normal temperatures, obtains curing component；By mass percentage, by 70% dimethylbenzene and 30%
Isobutanol stirs, and obtains diluent B, then by coating composition and curing component in mass ratio for 17:1 mixing, adds
Appropriate diluent B stirs, and obtains bio-oil modified epoxy anticorrosive paint after curing 15min.
Comparative example
This comparative example be the difference is that only with embodiment 7：Epoxy resin used is unmodified bisphenol A-type ring
Oxygen tree fat E51, and dilute bisphenol A type epoxy resin E51 with ethanol so as to bio-oil described in solids content and embodiment 7
The solids content of modified epoxy is identical.
Painting in the bio-oil modified epoxy anticorrosive paint and comparative example that prepare above-described embodiment 7
Material is applied on smooth aluminium sheet, the performance of test paint film, and test report is as shown in table 1.
Table 1 paint film property test report
As it can be seen from table 1 the toughness of bio-oil modified epoxy anticorrosive paint and shock resistance anti-cracking performance are excellent
In anti-corrosive paint of epoxy resin, it is mainly manifested in the 8th and the 9th two index.8th impact property, its value shows more greatly to paint
The shock resistance anti-cracking performance of film is better, the 9th bending property, and its value is less to represent that the crooking ability of paint film is better, toughness
Better.Secondly, the weatherability of bio-oil modified epoxy anticorrosive paint has compared with anti-corrosive paint of epoxy resin and significantly carries
Height, this can be seen that from the UV resistant performance of the 16th.In addition, the attachment of bio-oil modified epoxy anticorrosive paint
Power pull-out strength is also big compared with anti-corrosive paint of epoxy resin, and hydrophobicity is also improved, and drying time accelerates it is seen then that biological
The combination property of matter oil modified epoxy anticorrosive paint is significantly improved.Can be seen that life from above-mentioned test report
Material oil modified epoxy anticorrosive paint has excellent toughness, antiseptic property, shock resistance anti-cracking performance and weather resistance.
Claims (10)
1. a kind of bio-oil modified epoxy anticorrosive paint is it is characterised in that including coating composition and curing component, described
Coating composition includes the raw material of following mass percent：30～43% bio-oil modified epoxies, 5～15% organic molten
Agent, 0.1～0.5% coloring pigment, 35～58% extender pigments, 2～8% corrosion-inhibitive pigments, 0.3～2.8% thixotropic agent, 0.1
～0.8% dispersant and 0.1～0.9% defoamer, the mass percent sum of each raw material is 100%.
2. a kind of bio-oil modified epoxy anticorrosive paint according to claim 1 is it is characterised in that described biology
The preparation method of matter oil modified epoxy, its step is：By weight, by 50～100 parts of epoxy resin, diluent A 20
～80 parts sequentially add to reactor with 20～100 parts of bio-oil, start reactor stirring, are to slowly warm up to 50～65
DEG C, add 0.2～1.5 part of base catalyst, be heated to 60～75 DEG C and be incubated 0.5～2.0h, add metallic salt catalyst
0.1～0.8 part, after being heated to 75～85 DEG C, flow back and be incubated 0.5～2.0h, cooling obtains bio-oil modified epoxy.
3. a kind of bio-oil modified epoxy anticorrosive paint according to claim 1 and 2 is it is characterised in that described
The preparation method of bio-oil is as follows：
(1) extract：By weight, the living beings 20～100 parts of commercially available lignin, cellulose and hemicellulose being cracked and coming
Crude oil is added in container, adds 20～80 parts of stirrings of distilled water, and is warming up to 40～50 DEG C, is incubated 20～60min, standing point
Layer simultaneously removes supernatant liquor, adds 10～50 parts of stirrings of distilled water, and is warming up to 60～80 DEG C, is incubated 20～60min, standing point
Layer simultaneously removes supernatant liquor；
(2) distill：By weight, the bio-oil (1) being extracted is heated to 80～105 DEG C, vacuum distillation, removes moisture,
10～50 parts of diluent A is added to obtain bio-oil.
4. a kind of bio-oil modified epoxy anticorrosive paint according to claim 1 and 2 is it is characterised in that described
Epoxy resin include bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, phenol aldehyde type epoxy resin and
One of resorcinol type epoxy.
5. a kind of bio-oil modified epoxy anticorrosive paint according to claim 1 and 2 is it is characterised in that alkalescence
Catalyst is one of potassium hydroxide, NaOH, calcium acetate, barium hydroxide and magnesium carboxylates, and metallic salt catalyst is three
One of iron chloride, boron chloride and aluminium isopropoxide, diluent A is selected from ethanol, n-butanol, butyl acetate, acetic acid second
One or more of ester, oxolane, ethylene glycol and glycerine.
6. a kind of bio-oil modified epoxy anticorrosive paint according to claim 1 is it is characterised in that described solidification
Component includes the raw material of following mass percent：70～90% amine hardeners, 1～2.5% epoxy accelerator and 9～21% are organic
Solvent, the mass percent sum of each raw material is 100%.
7. a kind of bio-oil modified epoxy anticorrosive paint according to claim 1 or 6 is it is characterised in that described
Organic solvent includes one or more of acetone, n-butanol, butyl acetate, toluene, dimethylbenzene and oxolane, coloring pigment
Including one or more of titanium dioxide, iron oxide red, iron oxide yellow, carbon black and chrome green, extender pigment includes talcum powder, mica
One or more of powder, aluminium hydroxide and bentonite, corrosion-inhibitive pigments include the mixing of zinc powder or aluminium powder or zinc powder and aluminium powder
Thing, thixotropic agent includes one or more of organobentonite, kaolin and silica, and dispersant is wetting dispersing agent, disappears
Infusion is organic silicon defoamer.
8. a kind of bio-oil modified epoxy anticorrosive paint according to claim 6 is it is characterised in that described amine is solid
Agent includes in phenol aldehyde modified amine T31,650 polyamide, 651 polyamide, 701 phenol aldehyde modified amine and 702 phenol aldehyde modified amine
Plant or multiple, epoxy accelerator includes one or more of triethanolamine, dimethylaniline and DMP-30.
9. a kind of preparation method of bio-oil modified epoxy anticorrosive paint is it is characterised in that comprise the following steps：
A described bio-oil modified epoxy is mixed by () with 3～10% organic solvents, add coloring pigment, extender pigment,
Corrosion-inhibitive pigments, thixotropic agent, dispersant and defoamer, the rotating speed pressing 1500～3000 turns/min at 45～55 DEG C disperses at a high speed
30min, adds 2～5% organic solvents, stirs, and curing obtained coating composition after 1 day；
B amine hardener, epoxy accelerator and organic solvent are mixed by (), stir at normal temperatures, obtain curing component；
C () prepares anticorrosive paint：Coating composition and curing component are pressed (10～17):1 mass ratio mixing, adds diluent B
Stir, after curing 15min, obtain bio-oil modified epoxy anticorrosive paint.
10. the preparation method of a kind of bio-oil modified epoxy anticorrosive paint according to claim 9, its feature exists
In described diluent B group by mass percentage is divided into 50～80% dimethylbenzene and 20～50% isobutanols, the quality of each component
Percentage sum is 100%.
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| CN106398464B (en) | 2018-11-09 |
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Effective date of registration: 20200401 Address after: 618000 northwest side of national highway 108, Jinshan Industrial Park, Luojiang District, Deyang City, Sichuan Province Patentee after: Sichuan Jingwen Material Technology Co., Ltd Address before: 620000 Sichuan city in Meishan Province Economic Development Zone North East Logistics main road No. MJDA-037 Patentee before: SICHUAN GAONENG HI-TECH BIOLOGICAL RESIN Co.,Ltd. |