CN108997905A - A kind of preparation method of aqueous alkide resin - Google Patents
A kind of preparation method of aqueous alkide resin Download PDFInfo
- Publication number
- CN108997905A CN108997905A CN201811078438.6A CN201811078438A CN108997905A CN 108997905 A CN108997905 A CN 108997905A CN 201811078438 A CN201811078438 A CN 201811078438A CN 108997905 A CN108997905 A CN 108997905A
- Authority
- CN
- China
- Prior art keywords
- parts
- added
- aqueous alkide
- alkide resin
- oil
- 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.)
- Pending
Links
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
- 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
- C09D167/08—Polyesters modified with higher fatty oils or their acids, or with natural resins or resin acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/46—Polyesters chemically modified by esterification
- C08G63/48—Polyesters chemically modified by esterification by unsaturated higher fatty oils or their acids; by resin acids
-
- 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
-
- 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
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/328—Phosphates of heavy metals
-
- 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)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses a kind of preparation methods of aqueous alkide resin, belong to chemical technology field.It can occur local esterification between alkyd resin and amino resins prepared by the present invention and high density is crosslinked, form the double-deck reticular structure, after metallic substrate surface, the hydrophilic radical of the double-deck reticular structure is towards in interlayer in aqueous alkide resin, after aqueous alkide resin and amino resins are locally esterified in the present invention, at the interface of the two condensed phase, there are peptide bonds, peptide bond is easy hydrolysis water suction, and the outer layer that the double-deck reticular structure is formed after being esterified has hydrophobic ester group, essential oil volatility is extremely strong in essential oil microcapsules, essential oil can be slowly released from microcapsules, the microemulsified in the water phase of aqueous alkide resin, the drop of water is set to become smaller, convenient for solvent volatilization, rapid curing film forming, the hydrophobicity of essential oil is also beneficial to the volatilization of water in aqueous alkide resin, surface drying time shortens when solidifying aqueous alkide resin, form high adhesion force Paint film has broad application prospects.
Description
Technical field
The invention discloses a kind of preparation methods of aqueous alkide resin, belong to chemical technology field.
Background technique
Alkyd resin refers to introduces fatty acid side chain in the polyester, i.e., with a kind of fatty acid modified polyester.Water alcohol acid
Resin is primary raw material because using reproducible vegetable oil or fatty acid, and is taken water as a solvent, and VOC content is low, not only complies with
Requirement of the epoch to environmental protection, and reduce the consumption because using organic solvent to petroleum；Secondly, aqueous alkide resin point
Carbohydrate content is high in minor structure, molecular polarity is low, adjustability is strong, is used widely in industrial coating, can be used not only as
Metal, the priming paint of timber and frosting, finishing coat and single layer coating, it may also be used for ship, instrument, office equipment, metal building
The corrosion-resistant coating and protection of material etc..
Water soluble alkyd resin is solvable through one kind made of polycondensation polyalcohol, polyacid and vegetable oil (or fatty acid)
In the alkyd resin of water.In order to keep manufactured alkyd resin water-soluble, it is necessary to control its acid value and molecular weight.Water-soluble alcohol
Most of acid resin be high acid value, low cat degree resin, more contracting polyalcohol (such as multicondensed ethylene glycol, 2-glycidyls can also be used
Deng) to be improved by means of the dissolution assistant effect of ether it water-soluble or part polyacid is added can similarly have obvious effects on.
Water soluble alkyd resin is one of necessary kind of water-soluble resin, can be made into various air dryings and low temperature is dried in paint.
With vegetable oil (such as castor oil, soya-bean oil, linseed oil) or fatty acid (such as linseed fatty acid, soy(a)-bean oil fatty acid,
Coco-nut oil fatty acid, Castor Oil Fatty Acid etc.) it is modified, by polyalcohol (such as glycerol, pentaerythrite, three hydroxyls) and polyacid is (such as
Phthalic anhydride, isophthalic, cis-butenedioic anhydride etc.) esterification and the alkyd resin that synthesizes, including stemness, semi-drying and non-drying oil resin, have long oil,
Point of oil content, has good gloss and dispersibility, is the main film forming of many class coating such as alkyd, amino, nitro, polyurethane
Substance is widely used in all kinds of coating.Alkyd resin has stemness, gloss, flexibility, construction good to the wettability of pigment
It has excellent performance, the features such as coating is plentiful, decorative outstanding.In addition, the production of alkyd resin is independent of petroleum industry, not vulnerable to
Cheap to the influence of International Petroleum Price, adjustable between alkyd resin each component, the degree of branching, degree of functionality are variable, product transformation
Put into cycle of turnover it is short the advantages that, these are all that other resins cannot compare.
When aqueous alkide resin is applied to aqueous alkide resin at present, when solidification, paint film after surface drying time is long and solidification
Adhesive force is low, and corrosion resistance is poor.Therefore, invent that a kind of adhesion is good and the aqueous alkide resin of corrosion resistance and good is to change
Work technical field has positive effect.
Summary of the invention
Present invention mainly solves the technical issues of, for current aqueous alkide resin be applied to aqueous alkide resin when, Gu
When change, paint film adhesion is low after surface drying time length and solidification, and the poor defect of corrosion resistance provides a kind of aqueous alcoholic
The preparation method of acid resin.
In order to solve the above-mentioned technical problem, the technical scheme adopted by the invention is that:
A kind of preparation method of aqueous alkide resin, it is characterised in that specific preparation step are as follows:
(1) be added into the three-necked flask with dropping funel and condensing unit 70~80mL castor oil, 4~5g sodium methoxide, 5~
7mL triethanolamine, heat temperature raising, starting blender is stirred with the revolving speed of 200~300r/min, then is added into three-necked flask
Enter 40~50mL glycerol, insulated and stirred reaction obtains glycerolysis castor oil；
(2) 80~90mL hexamethylene diisocyanate is added into above-mentioned three-necked flask, the reaction was continued 2~3h cools down to three-necked flask,
10~15mL diethyl phosphate, 20~30mL glycerol and 20~25mL maleic anhydride are successively added into three-necked flask, by 3~
5mL dibutyl tin dilaurate pours into constant pressure funnel after being dissolved in 35~40mL acetone, instills in three-necked flask, when being added dropwise
Heating, after heating, the reaction was continued 3~4h obtains polyurethane based on castor oil；
(3) according to parts by weight, by 30~40 parts of polyurethane based on castor oil, 10~20 parts of trimethylolpropanes, 10~12 parts of rings
Oxygen soybean oil and 0.5~0.8 part of dibutyl tin dilaurate are added in four-hole boiling flask, and oil bath heating heats up under nitrogen protection
Afterwards, start blender, with the revolving speed insulated and stirred of 300~350r/min, reaction obtains alcoholysis product；
(4) according to parts by weight, it continues up and states 10~15 parts of M-phthalic acids of addition in four-hole boiling flask, oil bath heating heating,
Insulation reaction, cooling, be added 8~10 parts of inclined benzoic anhydrides, after cooling, into four-hole boiling flask be added 20~30 parts of propylene glycol monomethyl ethers into
Row dilution, continues to cool down, and triethylamine and distilled water is added, and discharging obtains alkyd resin after stirring 20~25min；
(5) according to parts by weight, it takes 20~25 parts of beer waste yeasts to be put into supercentrifuge to be centrifuged, discards supernatant liquor, obtain
To milky yeast milk, milky yeast milk and thyme essential oil are mixed to get latex oil, wash latex oil 2 with dehydrated alcohol
~3 times, it is subsequently placed into drying in vacuum oven, obtains essential oil microcapsules；
(6) alkyd resin is mixed with amino resins, obtains hybrid resin, according to parts by weight, take 70~80 parts of hybrid resins,
5~10 parts of dimethyl silicone polymers, 8~12 parts of isophorones, 3~4 parts of triethanolamines, 4~5 parts of essential oil microcapsules are placed in high speed
In dispersion machine, high speed dispersion obtains aqueous alkide resin.
Temperature is 50~60 DEG C after heat temperature raising described in step (1), and the insulated and stirred reaction time is 3~4h.
Three-necked flask described in step (2) cooling after temperature be 50~60 DEG C, constant pressure funnel drop rate be 2~
3mL/min, control heating rate are 3~5 DEG C/min, and temperature is 80~82 DEG C after heating.
Temperature is 180~200 DEG C after the heating of oil bath heating described in step (3), and the insulated and stirred reaction time is 2~3h.
Oil bath heating warming temperature described in step (4) is 230~235 DEG C, and the insulation reaction time is 1~2h, for the first time
Temperature is 180~185 DEG C after cooling, and it is 110~120 DEG C that temperature after cooling down is added after inclined benzoic anhydride second, and propylene glycol is added
Temperature is 80~85 DEG C after third time cools down after methyl ether is diluted, and triethylamine and distilled water is added until reacting in four-hole boiling flask
Liquid pH is 8.0~8.5.
High speed centrifugation revolving speed described in step (5) is 5000~5500r/min, and centrifugation time is 10~15min, milky
Yeast milk and thyme essential oil mixed volume ratio are 2 ︰ 5, and vacuum oven set temperature is 35~45 DEG C, drying time is 3~
4h。
Alkyd resin described in step (6) and amino resins mixing mass ratio are 2 ︰ 1, high speed dispersion revolving speed is 3000~
3500r/min, jitter time are 15~20min.
The beneficial effects of the present invention are:
(1) present invention under the action of sodium methoxide and catalyst compounded triethanolamine with glycerol by castor oil catalyzed alcoholysis, obtain
Hexamethylene diisocyanate, diethyl phosphate, maleic anhydride, glycerol etc. are added into glycerolysis castor oil for glycerolysis castor oil
Raw material, graft reaction obtain polyurethane based on castor oil, by polyurethane based on castor oil, trimethylolpropane and di lauric dibutyl
Tin mixing, heating alcohol solution obtains alcoholysis product, is added phthalic acid into alcoholysis product, inclined benzoic anhydride, with third after insulation reaction
Glycol methyl ether, which is diluted, to be adjusted pH again and obtains alkyd resin, and alkyd resin is mixed with amino resins by certain mass ratio, is obtained
It is mixed to hybrid resin, then by trbasic zinc phosphate and mica powder, rust resisting pigment is obtained, by hybrid resin, dimethyl silicone polymer, different Buddhist
The raw materials such as your ketone, antirust filler, triethanolamine are placed in high speed disperser, and high speed dispersion obtains aqueous alkide resin, the present invention
It can occur local esterification between the alkyd resin and amino resins of preparation and high density is crosslinked, form the double-deck reticular structure,
After metallic substrate surface, the hydrophilic radical of the double-deck reticular structure is towards in interlayer in aqueous alkide resin, aqueous solvent
It can be gathered between the double-deck reticular structure, aqueous alkide resin surfaces externally and internally is made to form hydrophobic oily phase, improve water alcohol acid tree
The acid and alkali-resistance solvent corrosion performance of rouge precuring paint film, and contact of the metal base with aqueous vapor is avoided, prevent metal to be corroded；
(2) after aqueous alkide resin and amino resins are locally esterified in the present invention, at the interface of the two condensed phase, there are peptide bond, peptides
Key is easy hydrolysis water suction, and the outer layer for forming the double-deck reticular structure after being esterified has hydrophobic ester group, even if in humid air
Protected metal by the erosion of water, will not be close to metal internal layer amino resins in the double-deck reticular structure has good
Insulation performance generates weak current, and quickly so that outer bound pair coating system generates electrophilic or electron effect in the coating
To air dissipation electronics or capture electronics and weaken system electric current, corrosion current is difficult to generate, and improves the anti-of aqueous alkide resin
Rotten performance, activity is stronger when epoxidized soybean oil is reacted with maleic anhydride, shortens the curing time of aqueous alkide resin, epoxy is big
Double bond crosslinking occurs for soya-bean oil and maleic anhydride, forms oligomer, in the oligomer solidification process easily with metal base coating metal
It is complexed, so that the molecular force between metal and aqueous alkide resin is improved, paint film after solidifying aqueous alkide resin
Adhesive force greatly improves, in addition, essential oil volatility is extremely strong in essential oil microcapsules, essential oil can be slowly released from microcapsules,
Then the microemulsified in the water phase of aqueous alkide resin, makes the drop of water become smaller, and volatilizees convenient for solvent, rapid curing film forming, and
And the hydrophobicity of essential oil is also beneficial to the volatilization of water in aqueous alkide resin, thus surface drying time when solidifying aqueous alkide resin
Shorten, forms the paint film of high adhesion force, have broad application prospects.
Specific embodiment
70~80mL castor oil, 4~5g sodium methoxide, 5 are added into the three-necked flask with dropping funel and condensing unit
~7mL triethanolamine is heated to 50~60 DEG C, and starting blender is stirred with the revolving speed of 200~300r/min, then to
40~50mL glycerol is added in three-necked flask, insulated and stirred reacts 3~4h, obtains glycerolysis castor oil；It is burnt to above-mentioned three mouthfuls
80~90mL hexamethylene diisocyanate is added in bottle, the reaction was continued 2~3h is cooled to 50~60 DEG C to three-necked flask, successively to three
10~15mL diethyl phosphate, 20~30mL glycerol and 20~25mL maleic anhydride is added in mouth flask, by 3~5mL, bis- laurel
Sour dibutyl tin pours into constant pressure funnel after being dissolved in 35~40mL acetone, instills three mouthfuls of burnings with the drop rate of 2~3mL/min
In bottle, heat up when being added dropwise, control heating rate is 3~5 DEG C/min, is warming up to 80~82 DEG C, and the reaction was continued 3~4h is obtained
Polyurethane based on castor oil；According to parts by weight, by 30~40 parts of polyurethane based on castor oil, 10~20 parts of trimethylolpropanes, 10
~12 parts of epoxidized soybean oils and 0.5~0.8 part of dibutyl tin dilaurate are added in four-hole boiling flask, and oil bath adds under nitrogen protection
After heat is warming up to 180~200 DEG C, start blender, with the revolving speed insulated and stirred of 300~350r/min, reacts 2~3h, obtain
Alcoholysis product；According to parts by weight, it continues up and states 10~15 parts of M-phthalic acids of addition in four-hole boiling flask, oil bath heating heating
To 230~235 DEG C, 1~2h of insulation reaction, it is cooled to 180~185 DEG C, 8~10 parts of inclined benzoic anhydrides are added, it is cooled to 110~
After 120 DEG C, 20~30 parts of propylene glycol monomethyl ethers are added into four-hole boiling flask and are diluted, continues to be cooled to 80~85 DEG C, be added three
Ethamine and distilled water are until reaction solution pH is 8.0~8.5 in four-hole boiling flask, and discharging obtains alkyd resin after stirring 20~25min；
According to parts by weight, it takes 20~25 parts of beer waste yeasts to be put into supercentrifuge, is centrifuged with the revolving speed of 5000~5500r/min
10~15min discards supernatant liquor, obtains milky yeast milk, is by volume with thyme essential oil by milky yeast milk
2 ︰ 5 are mixed to get latex oil, are washed latex oil 2~3 times with dehydrated alcohol, are subsequently placed into the vacuum that set temperature is 35~45 DEG C
Dry 3~4h, obtains essential oil microcapsules in drying box；With amino resins in mass ratio it is that 2 ︰ 1 are mixed by alkyd resin, is mixed
Resin, according to parts by weight, take 70~80 parts of hybrid resins, 5~10 parts of dimethyl silicone polymers, 8~12 parts of isophorones,
3~4 parts of triethanolamines, 4~5 parts of essential oil microcapsules are placed in high speed disperser, with the revolving speed high speed point of 3000~3500r/min
15~20min is dissipated, aqueous alkide resin is obtained.
70mL castor oil, 4g sodium methoxide, tri- ethyl alcohol of 5mL are added into the three-necked flask with dropping funel and condensing unit
Amine is heated to 50 DEG C, and starting blender is stirred with the revolving speed of 200r/min, then addition 40mL is sweet into three-necked flask
Oil, insulated and stirred react 3h, obtain glycerolysis castor oil；80mL hexamethylene diisocyanate is added into above-mentioned three-necked flask, after
Continuous reaction 2h, is cooled to 50 DEG C to three-necked flask, be successively added into three-necked flask 10mL diethyl phosphate, 20mL glycerol and
20mL maleic anhydride pours into constant pressure funnel after 3mL dibutyl tin dilaurate is dissolved in 35mL acetone, with 2mL/min's
Drop rate instills in three-necked flask, heats up when being added dropwise, and control heating rate is 3 DEG C/min, is warming up to 80 DEG C, the reaction was continued
3h obtains polyurethane based on castor oil；According to parts by weight, by 30 parts of polyurethane based on castor oil, 10 parts of trimethylolpropanes, 10 parts
Epoxidized soybean oil and 0.5 part of dibutyl tin dilaurate are added in four-hole boiling flask, and oil bath heating is warming up to 180 under nitrogen protection
After DEG C, start blender, with the revolving speed insulated and stirred of 300r/min, reacts 2h, obtain alcoholysis product；According to parts by weight, after
Continue 10 parts of M-phthalic acids of addition, oil bath heating into above-mentioned four-hole boiling flask and be warming up to 230 DEG C, insulation reaction 1h is cooled to 180
DEG C, 8 parts of inclined benzoic anhydrides are added, after being cooled to 110 DEG C, 20 parts of propylene glycol monomethyl ethers is added into four-hole boiling flask and are diluted, continue
It is cooled to 80 DEG C, triethylamine and distilled water is added until reaction solution pH is 8.0 in four-hole boiling flask, stir to discharge after 20min and obtain
Alkyd resin；According to parts by weight, it takes 20 parts of beer waste yeasts to be put into supercentrifuge, is centrifuged with the revolving speed of 5000r/min
10min discards supernatant liquor, obtains milky yeast milk, with thyme essential oil is by volume that 2 ︰ 5 are mixed by milky yeast milk
Conjunction obtains latex oil, washs latex oil 2 times with dehydrated alcohol, is subsequently placed into dry in the vacuum oven that set temperature is 35 DEG C
3h obtains essential oil microcapsules；With amino resins in mass ratio it is that 2 ︰ 1 are mixed by alkyd resin, obtains hybrid resin, by weight
Number meter, takes 70 parts of hybrid resins, 5 parts of dimethyl silicone polymers, 8 parts of isophorones, 3 parts of triethanolamines, 4 parts of essential oil microcapsules to set
In high speed disperser, with the revolving speed high speed dispersion 15min of 3000r/min, aqueous alkide resin is obtained.
75mL castor oil, 4g sodium methoxide, tri- ethyl alcohol of 6mL are added into the three-necked flask with dropping funel and condensing unit
Amine is heated to 55 DEG C, and starting blender is stirred with the revolving speed of 250r/min, then addition 45mL is sweet into three-necked flask
Oil, insulated and stirred react 3.5h, obtain glycerolysis castor oil；85mL hexamethylene diisocyanate is added into above-mentioned three-necked flask,
The reaction was continued 2.5h, is cooled to 55 DEG C to three-necked flask, and 12mL diethyl phosphate, 25mL glycerol are successively added into three-necked flask
With 22mL maleic anhydride, constant pressure funnel is poured into after 4mL dibutyl tin dilaurate is dissolved in 37mL acetone, with 2mL/min
Drop rate instill in three-necked flask, heat up when being added dropwise, control heating rate is 4 DEG C/min, is warming up to 81 DEG C, and continuation is instead
3.5h is answered, polyurethane based on castor oil is obtained；According to parts by weight, by 35 parts of polyurethane based on castor oil, 15 parts of trimethylolpropanes,
11 parts of epoxidized soybean oils and 0.6 part of dibutyl tin dilaurate are added in four-hole boiling flask, and oil bath heating heats up under nitrogen protection
To after 190 DEG C, start blender, with the revolving speed insulated and stirred of 320r/min, reacts 2.5h, obtain alcoholysis product；By weight
Number meter continues up and states in four-hole boiling flask 12 parts of M-phthalic acids of addition, and oil bath heating is warming up to 232 DEG C, insulation reaction 1.5h,
182 DEG C are cooled to, 9 parts of inclined benzoic anhydrides are added, after being cooled to 115 DEG C, 25 parts of propylene glycol monomethyl ethers is added into four-hole boiling flask and carry out
Dilution continues to be cooled to 82 DEG C, and triethylamine and distilled water is added until reaction solution pH is 8.2 in four-hole boiling flask, after stirring 22min
Discharging obtains alkyd resin；According to parts by weight, 22 parts of beer waste yeasts are taken to be put into supercentrifuge, with 5200r/min's
Revolving speed is centrifuged 12min, discards supernatant liquor, obtains milky yeast milk, and milky yeast milk and thyme essential oil are pressed volume
Than being mixed to get latex oil for 2 ︰ 5, latex oil is washed 2 times with dehydrated alcohol, it is dry to be subsequently placed into the vacuum that set temperature is 40 DEG C
Dry 3.5h, obtains essential oil microcapsules in dry case；With amino resins in mass ratio it is that 2 ︰ 1 are mixed by alkyd resin, is mixed
Resin takes 75 parts of hybrid resins, 7 parts of dimethyl silicone polymers, 10 parts of isophorones, 3 parts of triethanolamines, 4 according to parts by weight
Part essential oil microcapsules are placed in high speed disperser, with the revolving speed high speed dispersion 17min of 3200r/min, obtain aqueous alkide resin.
80mL castor oil, 5g sodium methoxide, tri- ethyl alcohol of 7mL are added into the three-necked flask with dropping funel and condensing unit
Amine is heated to 60 DEG C, and starting blender is stirred with the revolving speed of 300r/min, then addition 50mL is sweet into three-necked flask
Oil, insulated and stirred react 4h, obtain glycerolysis castor oil；90mL hexamethylene diisocyanate is added into above-mentioned three-necked flask, after
Continuous reaction 3h, is cooled to 60 DEG C to three-necked flask, be successively added into three-necked flask 15mL diethyl phosphate, 30mL glycerol and
25mL maleic anhydride pours into constant pressure funnel after 5mL dibutyl tin dilaurate is dissolved in 40mL acetone, with 3mL/min's
Drop rate instills in three-necked flask, heats up when being added dropwise, and control heating rate is 5 DEG C/min, is warming up to 82 DEG C, the reaction was continued
4h obtains polyurethane based on castor oil；According to parts by weight, by 40 parts of polyurethane based on castor oil, 20 parts of trimethylolpropanes, 12 parts
Epoxidized soybean oil and 0.8 part of dibutyl tin dilaurate are added in four-hole boiling flask, and oil bath heating is warming up to 200 under nitrogen protection
After DEG C, start blender, with the revolving speed insulated and stirred of 350r/min, reacts 3h, obtain alcoholysis product；According to parts by weight, after
Continue 15 parts of M-phthalic acids of addition, oil bath heating into above-mentioned four-hole boiling flask and be warming up to 235 DEG C, insulation reaction 2h is cooled to 185
DEG C, 10 parts of inclined benzoic anhydrides are added, after being cooled to 120 DEG C, 30 parts of propylene glycol monomethyl ethers is added into four-hole boiling flask and are diluted, continue
It is cooled to 85 DEG C, triethylamine and distilled water is added until reaction solution pH is 8.5 in four-hole boiling flask, stir to discharge after 25min and obtain
Alkyd resin；According to parts by weight, it takes 25 parts of beer waste yeasts to be put into supercentrifuge, is centrifuged with the revolving speed of 5500r/min
15min discards supernatant liquor, obtains milky yeast milk, with thyme essential oil is by volume that 2 ︰ 5 are mixed by milky yeast milk
Conjunction obtains latex oil, washs latex oil 3 times with dehydrated alcohol, is subsequently placed into dry in the vacuum oven that set temperature is 45 DEG C
4h obtains essential oil microcapsules；With amino resins in mass ratio it is that 2 ︰ 1 are mixed by alkyd resin, obtains hybrid resin, by weight
Number meter, takes 80 parts of hybrid resins, 10 parts of dimethyl silicone polymers, 12 parts of isophorones, 4 parts of triethanolamines, 5 parts of essential oil microcapsules
It is placed in high speed disperser, with the revolving speed high speed dispersion 20min of 3500r/min, obtains aqueous alkide resin.
The aqueous alkide resin that comparative example is produced with company of Foshan City is as a comparison case to aqueous alcoholic produced by the present invention
Aqueous alkide resin in acid resin and comparative example carries out performance detection, and testing result is as shown in table 1:
Test method:
Surface drying time test is detected by GB/T1728 standard.
Adhesive force test is detected by GB/T 1720 " paint film adhesion measuring method " scratch.
Corrosion resistance test: after the aqueous alkide resin dried coating film in example 1~3 and comparative example, 25 DEG C are placed in
In 3%NaCl solution for 24 hours after, observe surface situation of change.
1 aqueous alkide resin performance measurement result of table
| Test item | Example 1 | Example 2 | Example 3 | Comparative example |
| Surface drying time (h) | 0.9 | 0.7 | 0.6 | 3.1 |
| Adhesive force (grade) | 0 | 0 | 0 | 3 |
| Resistance to salt water (25 DEG C of 3%NaCl solution, for 24 hours) | Change colour without the blistering that falls off, without corrugation | Change colour without the blistering that falls off, without corrugation | Change colour without the blistering that falls off, without corrugation | Obviously fall off blistering discoloration |
According to above-mentioned detection data, aqueous alkide resin surface drying time of the invention is short, and minimum needs 0.6h, and adhesive force is good,
Adhesive force grade is high, and paint film has broad application prospects without the blistering that falls off, no corrugation discoloration, good corrosion resistance.
Claims (7)
1. a kind of preparation method of aqueous alkide resin, it is characterised in that specific preparation step are as follows:
(1) 70~80mL castor oil, 4~5g sodium methoxide, 5 are added into the three-necked flask with dropping funel and condensing unit
~7mL triethanolamine, heat temperature raising, starting blender are stirred with the revolving speed of 200~300r/min, then into three-necked flask
40~50mL glycerol is added, insulated and stirred reaction obtains glycerolysis castor oil；
(2) 80~90mL hexamethylene diisocyanate is added into above-mentioned three-necked flask, the reaction was continued 2~3h cools down to three-necked flask,
10~15mL diethyl phosphate, 20~30mL glycerol and 20~25mL maleic anhydride are successively added into three-necked flask, by 3~
5mL dibutyl tin dilaurate pours into constant pressure funnel after being dissolved in 35~40mL acetone, instills in three-necked flask, when being added dropwise
Heating, after heating, the reaction was continued 3~4h obtains polyurethane based on castor oil；
(3) according to parts by weight, by 30~40 parts of polyurethane based on castor oil, 10~20 parts of trimethylolpropanes, 10~12 parts of rings
Oxygen soybean oil and 0.5~0.8 part of dibutyl tin dilaurate are added in four-hole boiling flask, and oil bath heating heats up under nitrogen protection
Afterwards, start blender, with the revolving speed insulated and stirred of 300~350r/min, reaction obtains alcoholysis product；
(4) according to parts by weight, it continues up and states 10~15 parts of M-phthalic acids of addition in four-hole boiling flask, oil bath heating heating,
Insulation reaction, cooling, be added 8~10 parts of inclined benzoic anhydrides, after cooling, into four-hole boiling flask be added 20~30 parts of propylene glycol monomethyl ethers into
Row dilution, continues to cool down, and triethylamine and distilled water is added, and discharging obtains alkyd resin after stirring 20~25min；
(5) according to parts by weight, it takes 20~25 parts of beer waste yeasts to be put into supercentrifuge to be centrifuged, discards supernatant liquor, obtain
To milky yeast milk, milky yeast milk and thyme essential oil are mixed to get latex oil, wash latex oil 2 with dehydrated alcohol
~3 times, it is subsequently placed into drying in vacuum oven, obtains essential oil microcapsules；
(6) alkyd resin is mixed with amino resins, obtains hybrid resin, according to parts by weight, take 70~80 parts of compound trees
Rouge, 5~10 parts of dimethyl silicone polymers, 8~12 parts of isophorones, 3~4 parts of triethanolamines, 4~5 parts of essential oil microcapsules are placed in
In high speed disperser, high speed dispersion obtains aqueous alkide resin.
2. a kind of preparation method of aqueous alkide resin according to claim 1, it is characterised in that: described in step (1)
Temperature is 50~60 DEG C after heat temperature raising, and the insulated and stirred reaction time is 3~4h.
3. a kind of preparation method of aqueous alkide resin according to claim 1, it is characterised in that: described in step (2)
Temperature is 50~60 DEG C after three-necked flask cooling, and constant pressure funnel drop rate is 2~3mL/min, and control heating rate is 3
~5 DEG C/min, temperature is 80~82 DEG C after heating.
4. a kind of preparation method of aqueous alkide resin according to claim 1, it is characterised in that: described in step (3)
Temperature is 180~200 DEG C after oil bath heating heating, and the insulated and stirred reaction time is 2~3h.
5. a kind of preparation method of aqueous alkide resin according to claim 1, it is characterised in that: described in step (4)
Oil bath heating warming temperature is 230~235 DEG C, and the insulation reaction time is 1~2h, and temperature is 180~185 after cooling down for the first time
DEG C, it is 110~120 DEG C that temperature after cooling down is added after inclined benzoic anhydride second, and third time after propylene glycol monomethyl ether is diluted is added
Temperature is 80~85 DEG C after cooling, and triethylamine and distilled water is added until reaction solution pH is 8.0~8.5 in four-hole boiling flask.
6. a kind of preparation method of aqueous alkide resin according to claim 1, it is characterised in that: described in step (5)
High speed centrifugation revolving speed is 5000~5500r/min, and centrifugation time is 10~15min, and milky yeast milk and thyme essential oil are mixed
Conjunction volume ratio is 2 ︰ 5, and vacuum oven set temperature is 35~45 DEG C, and drying time is 3~4h.
7. a kind of preparation method of aqueous alkide resin according to claim 1, it is characterised in that: described in step (6)
Alkyd resin and amino resins mixing mass ratio are 2 ︰ 1, and high speed dispersion revolving speed is 3000~3500r/min, jitter time 15
~20min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811078438.6A CN108997905A (en) | 2018-09-17 | 2018-09-17 | A kind of preparation method of aqueous alkide resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811078438.6A CN108997905A (en) | 2018-09-17 | 2018-09-17 | A kind of preparation method of aqueous alkide resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108997905A true CN108997905A (en) | 2018-12-14 |
Family
ID=64592540
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811078438.6A Pending CN108997905A (en) | 2018-09-17 | 2018-09-17 | A kind of preparation method of aqueous alkide resin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108997905A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110016278A (en) * | 2019-03-06 | 2019-07-16 | 常州市三伊化工有限公司 | A kind of preparation method of the anti-scratch black finish of dumb light |
| CN110408001A (en) * | 2019-06-21 | 2019-11-05 | 黄兰英 | A kind of preparation method of water-based polyurethane curing agent |
| CN110484109A (en) * | 2019-09-09 | 2019-11-22 | 马鞍山采石矶涂料有限公司 | A kind of aqueous maleic anhydride alkyd paint and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108017981A (en) * | 2017-12-29 | 2018-05-11 | 唐林元 | A kind of preparation method of quick-drying type metal anticorrosive paint |
| CN108034342A (en) * | 2017-12-23 | 2018-05-15 | 仇颖莹 | A kind of preparation method of corrosion-resistant water-based metal baking vanish |
-
2018
- 2018-09-17 CN CN201811078438.6A patent/CN108997905A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108034342A (en) * | 2017-12-23 | 2018-05-15 | 仇颖莹 | A kind of preparation method of corrosion-resistant water-based metal baking vanish |
| CN108017981A (en) * | 2017-12-29 | 2018-05-11 | 唐林元 | A kind of preparation method of quick-drying type metal anticorrosive paint |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110016278A (en) * | 2019-03-06 | 2019-07-16 | 常州市三伊化工有限公司 | A kind of preparation method of the anti-scratch black finish of dumb light |
| CN110408001A (en) * | 2019-06-21 | 2019-11-05 | 黄兰英 | A kind of preparation method of water-based polyurethane curing agent |
| CN110484109A (en) * | 2019-09-09 | 2019-11-22 | 马鞍山采石矶涂料有限公司 | A kind of aqueous maleic anhydride alkyd paint and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108997905A (en) | A kind of preparation method of aqueous alkide resin | |
| CN103224615B (en) | Alkyd resin composition and preparation method thereof | |
| CN102757551B (en) | Aqueous epoxy modified alkyd resin and preparation method and application thereof | |
| CN107674475B (en) | A kind of preparation method of low-temperature setting waterborne epoxy floor paint | |
| US4116902A (en) | Polyurethane-modified alkyd resin | |
| KR101011337B1 (en) | Water soluble acrylic - modified epoxy ester resin composition and method of preparing the same | |
| CN102757620A (en) | Heat-resistant phenolic resin produced by taking cresol residues as raw material and application of heat-resistant phenolic resin in heat-resistant anti-corrosion paint | |
| CN105622909B (en) | A kind of preparation method and applications of aqueous alkide resin | |
| CN103160099B (en) | Modified alkyd resin and preparation method thereof and two-component primer | |
| CN106010046B (en) | It is a kind of aluminum paint, aqueous and preparation method thereof | |
| CN113024821A (en) | Water-based alkyd acrylic hybrid resin and preparation method thereof | |
| CN107513340A (en) | A kind of self-drying aqueous alkyd paint of high rigidity and preparation method thereof | |
| CN106893087A (en) | A kind of aqueous polyester resin and preparation method thereof | |
| CN105968325B (en) | A kind of organosilicon modified polyester epoxy resin with resisting high-temperature yellowing performance | |
| CN108034342A (en) | A kind of preparation method of corrosion-resistant water-based metal baking vanish | |
| CN110204704A (en) | A kind of aqueous alkide resin of the group containing acetoacetyl and preparation method thereof | |
| CN107434946A (en) | A kind of preparation method of antibacterial organosol paint | |
| CN106939138B (en) | A kind of preparation method of antistripping oligomer waterborne epoxy coatings | |
| CN110157333A (en) | A kind of water-based anticorrosive paint and preparation method thereof | |
| CN106543836A (en) | A kind of water-based anticorrosive paint | |
| CN109627392A (en) | Fluoro- phosphate modified aqueous alkide resin of one kind and preparation method thereof | |
| CN110776630B (en) | Low-VOC silicon-containing modified waterborne alkyd resin and preparation method thereof | |
| CN106916517A (en) | A kind of aqueous polyester resin paint and preparation method thereof | |
| CN107556890A (en) | A kind of water alcohol acid coating and preparation method thereof | |
| WO1998046689A1 (en) | Low-emission curable printing-ink or coatings binders |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20181214 |
|
| RJ01 | Rejection of invention patent application after publication |