CN109679117A - The preparation method of latex of epoxy resin of aqueous phenolic aldehyde and coating composition comprising it - Google Patents
The preparation method of latex of epoxy resin of aqueous phenolic aldehyde and coating composition comprising it Download PDFInfo
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- CN109679117A CN109679117A CN201811377251.6A CN201811377251A CN109679117A CN 109679117 A CN109679117 A CN 109679117A CN 201811377251 A CN201811377251 A CN 201811377251A CN 109679117 A CN109679117 A CN 109679117A
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- Prior art keywords
- epoxy resin
- latex
- phenolic aldehyde
- aqueous phenolic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/07—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media from polymer solutions
-
- 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
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1477—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
- C09D163/04—Epoxynovolacs
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
- C08J2363/04—Epoxynovolacs
Abstract
The application proposes a kind of preparation method of latex of epoxy resin of aqueous phenolic aldehyde and the coating composition comprising it, a kind of preparation method of latex of epoxy resin of aqueous phenolic aldehyde comprising following steps: prepares liquid novolac epoxy resin；Aforesaid liquid novolac epoxy resin is dissolved in 1.4- dioxane and is heated to 50 DEG C -70 DEG C, then instills in hydramine and is warming up to 60 DEG C -85 DEG C, and constant temperature 2-3 hours；It is cooled to room temperature, glacial acetic acid is added dropwise and is neutralized into salt, add water to get latex of epoxy resin of aqueous phenolic aldehyde is arrived.Above-mentioned latex of epoxy resin of aqueous phenolic aldehyde is water-soluble, and preferably stability is preferable, and includes that its coating composition film adhesive, impact strength, hardness and the flexibility that are formed are preferable.
Description
Technical field
This application involves paint fields, and in particular, to a kind of preparation method of epoxy resin of aqueous phenolic aldehyde and includes it
Coating composition.
Background technique
Shrink sweet ether oil more the entitled line style phenolic aldehyde of novolac epoxy resin (EPN) chemistry, and sundown thick liquid is a kind of
Heat resistant type epoxy resin.Due to the epoxy group in novolac epoxy resin structure containing 2 or more, epoxy functionalities are high, can be with
It crosslinks and reacts with many types of curing agent, form tridimensional network, it is strong that solidfied material shows excellent machinery
Degree, electrical insulation capability, water resistance, chemical resistance, higher glass transition temperature and thermal stability[1]。
Traditional novolac epoxy resin coating can be released in production and work progress using organic solvent as dispersing agent
A large amount of toxic and harmful gas causes great harm environment and human health into atmosphere, and wastes a large amount of solvent
Resource has not met the environmental requirement of modern society.With the enhancing of environmental consciousness, countries in the world have been formulated sternly in succession
The legislations of environmental protection and policy of lattice, limit the discharge of volatile organic compounds (VOC), so that traditional solvent based coating
Development be increasingly restricted.
Summary of the invention
To solve the above-mentioned problems, the present invention proposes a kind of preparation method of latex of epoxy resin of aqueous phenolic aldehyde and comprising it
Coating composition.
A kind of preparation method of latex of epoxy resin of aqueous phenolic aldehyde comprising following steps:
Prepare liquid novolac epoxy resin；Aforesaid liquid novolac epoxy resin is dissolved in 1.4- dioxane and is heated
To 50 DEG C -70 DEG C, then instills in hydramine and be warming up to 60 DEG C -85 DEG C, and constant temperature 2-3 hours；It is cooled to room temperature, ice second is added dropwise
Acid is neutralized into salt, adds water to get latex of epoxy resin of aqueous phenolic aldehyde is arrived.
A kind of coating composition is solid comprising above-mentioned latex of epoxy resin of aqueous phenolic aldehyde, modified meerschaum, pigment and polyamide
Agent.
Due to introducing hydramine, hydrophilic radical is introduced for novolac epoxy resin, to make aqueous phenolic aldehyde obtained
Epoxy resin latex has preferable hydrophily.
Specific embodiment
Further illustrate that the present invention, these embodiments are only intended to illustrate the present invention below by embodiment and comparative example,
The present invention is not limited to following embodiments.All modifying or equivalently replacing the technical solution of the present invention, without departing from this hair
The spirit and scope of bright technical solution should all cover within the protection scope of the present invention.
The preparation method of the latex of epoxy resin of aqueous phenolic aldehyde provided according to a first aspect of the present invention is provided first.
A kind of preparation method of latex of epoxy resin of aqueous phenolic aldehyde comprising following steps:
Prepare liquid novolac epoxy resin；
Aforesaid liquid novolac epoxy resin is dissolved in 1.4- dioxane and is heated to 50 DEG C -70 DEG C, then instills alcohol
In amine and it is warming up to 60 DEG C -85 DEG C, and constant temperature 2-3 hours；
It is cooled to room temperature, glacial acetic acid is added dropwise and is neutralized into salt, add water to get latex of epoxy resin of aqueous phenolic aldehyde is arrived.
Optionally, described the step of preparing liquid novolac epoxy resin, includes:
Phenol is reacted 0.8-1.2 hours under the catalysis of dilute hydrochloric acid in 60~70 DEG C with formaldehyde, after decompression water removal, in alkali
Under the action of reacted at 80-120 DEG C 1.2-1.8 hours with epoxychloropropane, removal solvent obtain the liquid phenolic epoxy
Resin.Optionally, the alkali is sodium hydroxide or potassium hydroxide.
Optionally, the liquid phenolic epoxy resin: hydramine: the mass ratio of acetic acid is 72~83:12~22:1~11.
Optionally, the hydramine is diethanol amine or triethanolamine.
Optionally, in the instillation hydramine and the step of heating, 80 DEG C, and constant temperature 150 minutes are warming up to.
Secondly the coating group comprising above-mentioned latex of epoxy resin of aqueous phenolic aldehyde provided according to a second aspect of the present invention is provided
Close object.
The coating composition includes above-mentioned latex of epoxy resin of aqueous phenolic aldehyde, modified meerschaum, pigment and polyamide cure
Agent.
Optionally, the mass percent of the latex of epoxy resin of aqueous phenolic aldehyde is 48~58%, the modified meerschaum
Mass percent be 10~20%, the mass percent of the pigment is 1~9%, the quality hundred of the polyamide curing agent
Divide than being 22~32%.
Embodiment
The preparation of liquid phenolic epoxy resin
0.125mol phenol and 0.128mol formaldehyde under the catalysis of dilute HCL in 60~70 DEG C of reaction 1h, decompression water removal, then
Under the action of 5%NaOH, 1.5h vacuum distillation is reacted in 100 DEG C with the epoxychloropropane of 0.200mol and both obtains liquid phenolic ring
Oxygen resin.
The preparation of latex of epoxy resin of aqueous phenolic aldehyde
(1) 30g novolac epoxy resin is added in three-necked flask, makees solvent with 1.4- dioxane, is heated to 60 DEG C, stirs
It mixes and slowly instills diethanol amine after being completely dissolved novolac epoxy resin, after dripping off, it is continuously heating to certain temperature, constant temperature
2.5h。
(2) etc. room temperature is dropped to, glacial acetic acid is added dropwise, is neutralized into salt, adds a certain amount of water to get Modified phenolic epoxy resin
Water-based system.
The preparation of silane-modified sepiolite
(1) sepiolite original ore powder is added in the dilute hydrochloric acid of 1mol/L, magnetic agitation 2h by solid-to-liquid ratio 1: 10, is stood
After for 24 hours, takes upper layer suspension to filter, and be washed with deionized to neutrality, dried at 110 DEG C, it is levigate to obtain acid activation sea
Afrodite[17]。
(2) a certain amount of silane coupling agent is weighed, it is sufficiently mixed to pour into 95% ethanol solution that 100mL pH value is 3~5
Stirring 30min is closed, hydrolyzed silane solution is made.It weighs acid activation sepiolite and is mixed with deionized water by solid-to-liquid ratio 1: 10, ultrasound point
It after dissipating, pours into there-necked flask, stirs simultaneously water-bath the pre-heat treatment 30min.Then hydrolyzed silane solution is added, flows back at a certain temperature
Reaction, is stirred continuously in the process, is respectively washed 3 times after slurry after the reaction was completed is filtered with dehydrated alcohol and distilled water, removes
Unreacted silane coupling agent.Suspension again through suction filtration, drying, levigate obtain silane-modified sepiolite.
The influence of diethanol amine dosage
The hydrophily of modified resin derives from hydrophilic radical introduced in modified-reaction, the increase of hydrophilic group in molecule
The water-soluble enhancing of resin can so be made.As can be seen from Table 1, it is formed by 30g novolac epoxy resin and a certain amount of diethanol amine
Reaction system in, with the increase of diethanol amine dosage, system water solubility and water stability enhance.When diethanol amine
When dosage > 6.82g, stable, uniform, transparent epoxy resin aqueous solution can be formed；When its dosage is in 6g~6.82g, add water
It will form stable lotion to a certain extent；As diethanol amine dosage < 5g, formation emulsion intercalation method is poor, and placement has insoluble
Object is precipitated.This is because when open loop rate gradually decreases, the hydrophilic group in molecular resin subtracts with the reduction of diethanol amine dosage
Few, the molecular resin containing hydrophilic group and unmodified molecular resin form lotion in the form of self-emulsifying；With open loop rate
Be further reduced, the epoxy novolac molecule in emulsion particle increases, when the molecular resin containing hydrophilic group be not enough to emulsify it is unmodified
Resin when, resin is precipitated from water, it may appear that the phenomenon that agglomerating and precipitating.
1 diethanol amine of table and content of epoxy resin are on water-based system and the water-soluble influence of modified system
Note: novolac epoxy resin 30g in reaction system, 80 DEG C of reaction temperature, reaction time 150min.
The influence of reaction temperature
2 reaction temperature of table is on water-soluble influence
| Temperature/DEG C | 60 | 70 | 80 | 90 |
| Water solubility/g | 4.98 | 6.78 | Any ratio | Gel |
Note: the mass ratio of reaction time 150min, epoxy resin and diethanol amine is 4.4: 1, the matter of novolac epoxy resin
Amount is 30g.
During the modified-reaction of epoxy resin, the control of temperature is critically important, because of novolac epoxy resin and diethanol
The reaction of amine is exothermic reaction.Therefore, the water solubility for investigating modified resin under different temperatures is particularly important.As seen from Table 2, exist
In certain time, with the raising of reaction temperature, epoxy group conversion ratio is significantly improved.Because increasing temperature, the viscosity drop of system
It is low, be conducive to the contact and collision of molecule, increase the probability of effective collision to make reaction speed accelerate.But due to the reaction
It is exothermic reaction, when reaction speed is too fast, also than very fast, heat is difficult to pass out in time in system for heat release, causes anti-
The temperature of system is answered quickly to increase, meanwhile, during the reaction, open loop addition occurs for secondary amine and epoxy group in diethanol amine
It reacts and generates tertiary amine structure, it, which has, promotes the cured effect of cross linking of epoxy resin, thus when the temperature is excessively high, especially work as temperature
When degree is higher than 90 DEG C, it is easy to happen gelatin phenomenon；When temperature is lower, system viscosity will increase again, and each component is difficult to come into full contact with,
Reaction speed is slow.Therefore Comprehensive Experiment result and above-mentioned analysis, temperature are more suitable at 80 DEG C or so.
The influence of acetic acid dosage
3 acetic acid dosage of table is on aqueous systems stability and the hydrophilic influence of modified resin
Note: the matter of acetic acid is added in the modified resin that 30g novolac epoxy resin and the reaction of 6.82g diethanol amine generate
Amount.
Although introducing hydrophilic hydroxy group in modified resin molecule, resin does not still have water-soluble or water and dissipates at this time
Property.This is because the hydroxyl in resin forms hydrogen bond to each other, it is still within and forms and state.And after acetic acid is added, its meeting and add
Enter the tertiary amine structure of stage of reaction formation into salt, its essence is the tertiary amine nitrogens in the hydrogen ion and novolac epoxy resin molecule in acid
Atom with coordinate bond in conjunction with and generate the process of tertiary amine cation.When adding water, can ionize out strong aqueous tertiary amine salt cation and
Acetic acid anion, at the same also broken hydroxyl form and, thus make resin can be dispersed water in and form water-based system.By table 5
As can be seen that insufficient at salt degree, poorly water-soluble, stability is small when acetic acid dosage is few, and with the increase of acetic acid dosage, body
The water-soluble enhancing of system.But when acetic acid dosage is excessive, excessive acetic acid can destroy PART EPOXY base, and resin solidification is made to become tired
Difficulty, condensate performance are deteriorated.The dosage of comprehensive analysis, acetic acid should be best with 2.5g.
Influence of the addition of modified meerschaum to film
Sepiolite is aqueous magnesium silicate mineral, chemical formula Mg8Si12O30(OH)4(OH2)4·8H2O has chain
Shape and stratiform transiens structure feature, this special structure determine that it has good adsorptivity, rheological characteristic, ion exchange
Property and thermal stability, it is silane modified after sepiolite surface be modified, hydrophilicity is improved.Modified meerschaum is to film
Influence it is as shown in table 4:
Influence of 4 modified meerschaum of table to coating property
As shown in Table 3, the addition of modified meerschaum proposes film adhesive, impact strength, hardness and flexibility
It rises, but addition excessively can be such that the planarization on glossiness and surface is declined.Therefore, the percentage composition selection of modified meerschaum
15% than convenient.
Influence of the type and dosage of curing agent to film
Aqueous phenolic aldehyde epoxy emulsion system contains the functional groups such as hydroxyl, carboxyl and epoxy group, there is selfing in a heated condition
Join performance, but its crosslink density is lower, film comprehensive performance is poor, needs that curing agent is added to realize intermediate temperature setting.Selection
Tri- kinds of triethylene tetramine, m-phenylene diamine (MPD) and polyamide NP-300D curing agent are kept not by multiple repetition test in other conditions
Under the premise of change, influence of the different amine hardeners to paint solidification performance is probed into, film performance comparison is as shown in table 5:
The selection of 5 curing agent of table
As known from Table 5, compared with m-phenylene diamine (MPD), triethylene tetramine, after polyamide NP-300D solidification, film tool
There are higher hardness, adhesive force and excellent water resistance, resistance to salt water.It improves most significantly in flexibility, this is
Because polyamide NP-300D possesses certain flexible fatty carbon chain section, good suppleness can be provided.
N (amine active hydrogen): n (epoxy group) is higher, and the hardness and flexibility of film are higher and higher.This is because on the one hand
N (amine active hydrogen): n (epoxy group) improves, and increases the ratio of rigid chain segment in molecule after solidifying, thus hardness improves；Separately
On the one hand, n (amine active hydrogen): the raising of n (epoxy group) also increases the ratio of the fatty carbon chain in molecule space network, from
And flexibility is also with improve.When n (amine active hydrogen): when n (epoxy group) is lower, being crosslinked serious inadequate, network molecular structure
It is of a relatively loose, it is insufficiently resistant to the erosion of chemical reagent and the corrosion of external environment, film water-whitening resistant, adhesive force is lost.Cause
This, when n (amine active hydrogen): when n (epoxy group) is 1:1, film can obtain more comprehensive physical and chemical performance.
It is not for limiting claim, any this field skill although the application is disclosed as above with preferred embodiment
Art personnel without departing from the concept of this application, can make several possible variations and modification, therefore the application
Protection scope should be subject to the range that the claim of this application is defined.
Claims (8)
1. a kind of preparation method of latex of epoxy resin of aqueous phenolic aldehyde comprising following steps:
Prepare liquid novolac epoxy resin；
Aforesaid liquid novolac epoxy resin is dissolved in 1.4- dioxane and is heated to 50 DEG C -70 DEG C, then is instilled in hydramine
And 60 DEG C -85 DEG C are warming up to, and constant temperature 2-3 hours；
It is cooled to room temperature, glacial acetic acid is added dropwise and is neutralized into salt, add water to get latex of epoxy resin of aqueous phenolic aldehyde is arrived.
2. the preparation method of latex of epoxy resin of aqueous phenolic aldehyde as described in claim 1, which is characterized in that described to prepare liquid
The step of novolac epoxy resin includes:
Phenol is reacted 0.8-1.2 hours under the catalysis of dilute hydrochloric acid in 60 ~ 70 DEG C with formaldehyde, after decompression water removal, in the work of alkali
It is reacted at 80-120 DEG C 1.2-1.8 hours with lower with epoxychloropropane, removal solvent obtains the liquid phenolic epoxy resin.
3. the preparation method of latex of epoxy resin of aqueous phenolic aldehyde as described in claim 1, which is characterized in that the liquid phenolic
Epoxy resin: hydramine: the mass ratio of acetic acid is 72 ~ 83:12 ~ 22:1 ~ 11.
4. the preparation method of latex of epoxy resin of aqueous phenolic aldehyde as described in claim 1, which is characterized in that the hydramine is two
Ethanol amine or triethanolamine.
5. the preparation method of latex of epoxy resin of aqueous phenolic aldehyde as described in claim 1, which is characterized in that the instillation hydramine
In and the step of heat up in, be warming up to 80 DEG C, and constant temperature 150 minutes.
6. the preparation method of latex of epoxy resin of aqueous phenolic aldehyde as claimed in claim 2, which is characterized in that the alkali is hydrogen-oxygen
Change sodium or potassium hydroxide.
7. a kind of coating composition of the latex of epoxy resin of aqueous phenolic aldehyde comprising any one of such as claim 1-6, feature exist
In the coating composition includes latex of epoxy resin of aqueous phenolic aldehyde, the modified meerschaum, pigment such as any one of claim 1-5
And polyamide curing agent.
8. coating composition as claimed in claim 7, which is characterized in that the quality hundred of the latex of epoxy resin of aqueous phenolic aldehyde
Divide than being 48 ~ 58%, the mass percent of the modified meerschaum is 10 ~ 20%, and the mass percent of the pigment is 1 ~ 9%, institute
The mass percent for stating polyamide curing agent is 22 ~ 32%.
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| CN201811182550 | 2018-10-11 | ||
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Cited By (2)
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| CN112812273A (en) * | 2021-02-26 | 2021-05-18 | 美高微球(南通)科技有限公司 | Polyepoxy quaternary ammonium salt emulsion for cathode electrophoretic coating and preparation method and application thereof |
| CN114133535A (en) * | 2021-12-27 | 2022-03-04 | 安徽善孚新材料科技股份有限公司 | Moisture-heat-resistant epoxy resin and preparation method and application thereof |
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