CN112266453B - Phenol ether resin, coating composition containing same and preparation method thereof - Google Patents

Phenol ether resin, coating composition containing same and preparation method thereof Download PDF

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CN112266453B
CN112266453B CN202011420145.9A CN202011420145A CN112266453B CN 112266453 B CN112266453 B CN 112266453B CN 202011420145 A CN202011420145 A CN 202011420145A CN 112266453 B CN112266453 B CN 112266453B
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phenolic
resin
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ether resin
agent
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CN112266453A (en
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石磊
石轶砆
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Beijing Silver Sail Coating Corp ltd
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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
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/28—Chemically modified polycondensates
    • C08G8/36—Chemically modified polycondensates by etherifying
    • 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
    • C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
    • C09D161/04—Condensation polymers of aldehydes or ketones with phenols only
    • C09D161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C09D161/14—Modified phenol-aldehyde condensates
    • 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

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Abstract

The application provides a phenolic ether resin, an anticorrosive coating composition containing the same and a preparation method, wherein the phenolic ether resin is obtained by carrying out incomplete etherification condensation reaction on a phenolic resin, and is characterized in that the phenolic ether resin contains phenolic hydroxyl groups and epoxy ether groups, and the molar number of the phenolic hydroxyl groups is 5-600mol% of the epoxy ether groups. The anticorrosive coating composition disclosed by the application reasonably reduces the curing crosslinking density, reduces the internal stress generated in the drying process, and increases the flexibility, impact strength and vibration fatigue resistance of resin. The coating film has improved plasticity, temperature resistance, wet heat property and dry-wet alternation property, and shows good corrosion resistance at-40 to 150 ℃. The existence of phenolic hydroxyl can form a covalent bond with steel, improve the affinity of steel and greatly improve the bonding strength of the material, and the phenolic hydroxyl can ionize H+The ion has affinity to water or a wet surface, can be cured in a wet manner or in a wet manner, and has good application property.

Description

Phenol ether resin, coating composition containing same and preparation method thereof
Technical Field
The present invention relates to a phenol ether resin, a coating composition comprising the same, and a method for preparing the same. In particular to a coating composition capable of being applied with moisture and cured with moisture and a preparation method thereof.
Background
With the rapid development of economy and the increasing demand of petrochemical products, the petrochemical industry enters a new peak. From crude oil transportation, transfer storage, pipeline transportation, high-temperature equipment for refining and chemical industry and coal chemical industry to finished oil storage, the storage container is not optimistic in medium corrosion condition, and the existing anticorrosive coating can not meet the anticorrosive requirement.
In the field of corrosion prevention, along with the complication of a corrosion medium, the use environment temperature is continuously improved, more and more anticorrosive coatings produced by applying novolac epoxy resin are used, the novolac epoxy resin has a perfect molecular structure, is resistant to temperature, chemicals, water and acid and alkali salts, large in crosslinking density, bright in paint film, high in hardness, and capable of being dried at normal temperature, and the prepared coatings have good experimental data. However, the effect in practical application is often not good, which is quite different from the laboratory experiment result, and the equipment such as chemical heat-insulating pipelines, storage tanks, sewage storage pools and the like are damaged everywhere due to corrosion, and even cause great economic loss due to serious corrosion. The corrosion control and the corrosion prevention become a difficult problem in a high-temperature environment, a high-temperature medium and a complex chemical composition condition. There is a continuing effort by those skilled in the coatings industry to develop new coating products to meet the corrosion protection needs of the field.
Disclosure of Invention
The application provides an etherified modified phenolic resin, a coating composition containing the same and a preparation method thereof, and the method comprises the following embodiments:
embodiment 1. a phenol ether resin obtained by subjecting a phenol resin to an incomplete etherification condensation reaction, wherein the phenol ether resin contains a phenolic hydroxyl group and an epoxy ether group, and the phenolic hydroxyl group is 5 to 600mol%, for example 5 to 120 mol%, for example 100-600mol% of the epoxy ether group.
Embodiment 2. the phenol ether resin of embodiment 1, having the following structural formula:
Figure 150072DEST_PATH_IMAGE001
，
Figure 432149DEST_PATH_IMAGE002
，
Figure 821804DEST_PATH_IMAGE003
，
or a mixture comprising at least one of the foregoing.
Embodiment 3. the phenol ether resin of embodiment 1, wherein the phenolic hydroxyl groups are 5 to 120 mol% of the epoxy ether groups.
Embodiment 4. the phenol ether resin according to embodiment 1, wherein the molar number of the phenolic hydroxyl groups is 600mol% based on 100mol% of the epoxy ether groups.
Embodiment 5. the phenol ether resin of embodiment 1, wherein the structure of the phenolic resin comprises at least one selected from the group consisting of:
Figure 531134DEST_PATH_IMAGE004
，
Figure 137565DEST_PATH_IMAGE005
，
Figure 971136DEST_PATH_IMAGE006
。
embodiment 6. a method of making a phenol ether resin, comprising:
the phenol ether resin according to embodiment 1 is obtained by subjecting a phenol resin and epichlorohydrin to a condensation reaction.
Embodiment 7. the process of embodiment 6, wherein the moles of epichlorohydrin are less than the moles of phenolic hydroxyl groups in the phenolic resin.
Embodiment 8. the method of embodiment 7, wherein the phenolic hydroxyl groups in the phenolic resin are 105 to 700 mol%, such as 130 to 200mol%, of epichlorohydrin.
Embodiment 9. an anticorrosive coating composition comprising a first component comprising: the phenol ether resin of any one of embodiments 1 to 5, and one or more of the following components: a pigment, a filler, an auxiliary agent, a solvent, and a first auxiliary material; the second component comprises a curing agent and optionally a second adjuvant.
Embodiment 10. the composition of embodiment 9, wherein the pigment comprises one or more selected from the group consisting of: titanium dioxide, zinc powder, iron oxide red, micaceous iron oxide, aluminum powder, zinc oxide, zinc phosphate, graphite and aluminum polyphosphate; the filler comprises one or more selected from the group consisting of: static conductive powder, mica powder, titanium dioxide, barium sulfate, mica iron oxide, calcined kaolin, light calcium carbonate, barium sulfate, quartz powder, diatomite, pulverized coal floating beads and pulverized coal sinking beads; the adjuvant comprises one or more selected from the group consisting of: defoaming agent, flatting agent, dispersing agent, toughening agent, coupling agent, anti-settling agent, antioxidant and mildew preventive; the solvent comprises one or more selected from the group consisting of: xylene, n-butanol, lipid solvents and ketone solvents; the first excipient comprises one or more selected from the group consisting of: epoxy resin, novolac epoxy resin, silicone resin; the curing agent comprises one or more selected from the group consisting of: modified amine composite curing agent, polyamide, phenolic amine, aromatic amine, aliphatic amine and alicyclic amine; the second excipient comprises one or more selected from the group consisting of: ethanol, butanol and xylene or butyl acetate.
Embodiment 11 the composition of embodiment 10, wherein the phenolic ether resin and optionally the first adjuvant comprise 20 to 60 wt% of the first component, the pigment and filler comprise 20 to 46wt% of the first component, the adjuvant comprises 1 to 5wt% of the first component, the solvent comprises 0 to 50 wt% of the first component, the curing agent comprises 5 to 50 wt% of the first component,
embodiment 12. a method of making the composition of any one of embodiments 9 to 11, comprising:
preparing a phenol ether resin according to any one of embodiments 1 to 5;
mixing the phenolic ether resin and one or more selected from pigments, fillers, auxiliaries, solvents and first auxiliary materials to obtain a first component;
and mixing the curing agent and optional second auxiliary materials to obtain a second component.
The etherified modified phenolic resin and the anticorrosive coating composition containing the etherified modified phenolic resin have the following technical effects:
the coating has good temperature resistance, temperature change resistance, damp and heat resistance and dry and wet alternation resistance, and keeps good chemical resistance and corrosion resistance at the temperature of-40 to 150 ℃.
And (II) the paint has excellent adhesive force and substrate affinity, can be applied with moisture, cured with moisture, dried at low temperature, resists impact and vibration fatigue, and has stable performance and strong adaptability.
And (III) the application range is wide, and the method can be suitable for various chemical media: the corrosion prevention of storage tanks, pipelines, storage pools and other equipment for storing and transporting media such as methanol, ethanol, tert-butyl ether, ethanol gasoline, naphtha, crude oil, various finished oils, acid-base salt chemical wastewater, various chemical mixed liquids and the like.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present disclosure more apparent, the technical solutions of the present disclosure will be clearly and completely described below in conjunction with the embodiments of the present disclosure. It is to be understood that the described embodiments are only a few embodiments of the present disclosure, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the described embodiments of the disclosure without any inventive step, are within the scope of protection of the disclosure.
The present invention is directed to solving at least one of the problems of the prior art or the related art.
To this end, one aspect of the present invention provides a phenol ether resin obtained by subjecting a phenol resin to an incomplete etherification condensation reaction, wherein the phenol ether resin contains phenolic hydroxyl groups and epoxy ether groups, and the phenolic hydroxyl groups are present in a molar amount of 5 to 600mol%, such as 5 to 120 mol%, such as 20 to 200mol%, such as 40 to 80 mol%, such as 30 to 100mol%, based on the epoxy ether groups.
The term epoxy ether group as used herein refers to an ether group directly bonded to an alkylene oxide group. The incomplete etherification condensation reaction refers to that phenolic hydroxyl groups with a certain proportion are still remained after the etherification condensation reaction is carried out on the phenolic resin, and the number of epoxy ether groups is relatively reduced, so that the curing crosslinking density of the phenolic ether resin is reduced, the internal stress generated in the drying process is reduced, and the flexibility, the impact strength and the vibration fatigue resistance of the resin are improved. The plasticity, temperature resistance, wet heat property and dry-wet alternation of the paint film are improved. On the other hand, the existence of the phenolic hydroxyl can form a covalent bond with steel, the bonding strength of the material is greatly improved, meanwhile, the phenolic hydroxyl can ionize H + ions, has affinity to water or a moist surface, can be cured in a moist or wet manner, improves the affinity of steel and has good construction property. The incomplete etherification condensation reaction can also be obtained by carrying out incomplete etherification modification on the phenolic resin, namely the etherified modified phenolic resin obtained after carrying out etherification modification reaction on the phenolic resin still contains phenolic hydroxyl groups in a certain proportion.
The difference of the phenol ether resin compared with the novolac epoxy resin widely used at present is mainly as follows:
the prior phenolic epoxy resin has three types, namely the following structures:
Figure 464565DEST_PATH_IMAGE007
o-cresol type novolac epoxy resin
Figure 594064DEST_PATH_IMAGE008
Phenol type novolac epoxy resin
Figure 235261DEST_PATH_IMAGE009
Bisphenol A type novolac epoxy resin
The novolac epoxy resin has a too regular structure, lacks active groups except ether bonds, and has high cohesive force and poor affinity. In practical use, the crosslinking density is too high, the hardness is high, the internal stress generated in the drying process is large, and the elasticity, the temperature resistance, the moisture resistance and the dry-wet crosslinking property of a paint film are poor; the construction property is poor, the bonding strength is inferior to that of epoxy resin, the affinity with steel is poor at a lower temperature, even the construction cannot be carried out at an environmental temperature lower than 5 ℃, and the novolac epoxy resin is not bonded with metals such as copper. In the present application, the subscript "n" used to indicate the degree of polymerization of the polymer has a meaning generally understood by those skilled in the art, unless otherwise specified.
The resin structure is changed by redesigning the production process. The application limits that the mole number of the phenolic hydroxyl group in the phenolic ether resin is 5-600mol%, such as 5-120 mol%, such as 20-200 mol%, such as 40-80 mol%, such as 30-100mol% of the epoxy ether group, the phenolic ether resin obtained by the method contains a certain proportion of phenolic hydroxyl groups, and the anticorrosive paint product produced by using the phenolic ether resin as the base material of the anticorrosive paint can be suitable for the storage tank and pipeline corrosion prevention of media such as storage and transportation chemical raw materials, ethanol gasoline, naphtha, crude oil, various types of finished oil, acid and alkali industrial sewage, and has the characteristics of low curing temperature, strong adhesive force, heat resistance, temperature change resistance, alternate dry and wet resistance, good construction adaptability and the like.
In some embodiments, the phenolic ether resin has the following structural formula:
Figure 344293DEST_PATH_IMAGE010
，
Figure 207076DEST_PATH_IMAGE011
，
Figure 523788DEST_PATH_IMAGE012
，
or a mixture comprising at least one of the foregoing.
In some embodiments, the phenolic hydroxyl groups are present in a molar amount of 100-600mol%, such as 130-500 mol%, of the epoxy ether groups. The more the phenolic hydroxyl groups are, the lower the curing crosslinking density of the phenolic ether resin is, the lower the internal stress is, the stronger the flexibility of the resin is, and the phenolic hydroxyl groups can generate H+Ions can be compatible on the moist metal surface and generate Fe-O covalent bonds, so that the bonding strength of the coating is enhanced, the coating has better adhesive force on the moist metal surface, and the workability is improved. The number of phenolic hydroxyl groups can be chosen by those skilled in the art as appropriate to the coating performance requirements.
In some embodiments, the number of moles of phenolic hydroxyl groups is from 5 to 120 mole% of epoxy ether groups. The more the epoxy ether groups are, the higher the crosslinking density of the phenolic ether resin is, the harder the paint film is, the toughness is reduced, and the performance is closer to that of the novolac epoxy resin. The number of epoxy ether groups can be chosen by one skilled in the art as appropriate to the coating performance requirements.
In some embodiments, the phenolic resin comprises at least one selected from the group consisting of:
Figure 603346DEST_PATH_IMAGE013
，
Figure 217867DEST_PATH_IMAGE014
，
Figure 685888DEST_PATH_IMAGE015
。
in still another aspect of the present invention, there is provided a method for preparing a phenol ether resin, comprising: and carrying out condensation reaction on the phenolic resin and epoxy chloropropane to obtain the phenolic ether resin.
In some embodiments, the moles of epichlorohydrin are less than the moles of phenolic hydroxyl groups in the phenolic resin. According to the proportion of phenolic hydroxyl groups and epoxy ether groups in the raw materials in a specific proportion, the phenolic hydroxyl groups in the phenolic ether resin have the mole number of 5-600mol%, preferably 5-200mol%, more preferably 30-100mol% of the epoxy ether groups.
In some embodiments, the phenol ether resin is prepared by reacting an excess of phenolic resin with epichlorohydrin to obtain the phenol ether resin, wherein the phenolic hydroxyl group in the phenolic resin is 105 mol% to 700 mol%, such as 130 mol% to 200mol%, of the epichlorohydrin, so that the resulting phenol ether resin contains a certain proportion of phenolic hydroxyl groups.
In a third aspect of the present invention, there is provided an anticorrosive coating composition comprising a first component comprising: the etherified modified phenolic resin and one or more of the following components: a pigment, a filler, an auxiliary agent, a solvent, and a first auxiliary material; the second component comprises a curing agent and optionally a second adjuvant.
In some embodiments, the pigment comprises one or more selected from the group consisting of: titanium dioxide, zinc powder, iron oxide red, micaceous iron oxide, aluminum powder, zinc oxide, zinc phosphate, graphite and aluminum polyphosphate; the filler comprises one or more selected from the group consisting of: static conductive powder, mica powder, titanium dioxide, barium sulfate, mica iron oxide, calcined kaolin, light calcium carbonate, barium sulfate and quartz powder; in some embodiments, the filler may be colored to act as a pigment, which may also function as a filler, i.e., the pigment and filler may be substituted for each other. The adjuvant comprises one or more selected from the group consisting of: defoaming agent, flatting agent, dispersing agent, toughening agent, coupling agent, anti-settling agent, antioxidant and mildew preventive; the solvent comprises one or more selected from the group consisting of: xylene, n-butanol, lipid solvents and ketone solvents; the first excipient comprises one or more selected from the group consisting of: novolac epoxy resins, silicone resins, epoxy resins such as small molecule epoxy resins 696A, 660, and the like, F51 novolac epoxy resins; the paint prepared when the content of the small molecular epoxy resin is below 2 percent contains a solvent, the temperature resistance reaches 150 ℃, and when the content of the small molecular epoxy resin is above 5 percent, the prepared paint is a solvent-free product (the content of the solvent is below 2 percent), the temperature resistance is lower (about 120 ℃), but the VOC content is low, and the paint is environment-friendly. Accordingly, the present application also provides a solvent-free product, i.e., the anticorrosive coating composition described herein, wherein the composition contains 5wt% to 15wt% of a small molecule epoxy resin as the first auxiliary material, and the composition contains 2 wt% or less of a solvent. As used herein, a "small molecule epoxy resin" refers to an epoxy resin having a molecular weight of less than 500. Existing small molecule epoxy products include those commercially available under the trade name epoxy activator 660A or epoxy activator 696A.
The curing agent and the second auxiliary material used in the present application are not particularly limited and may be selected by those skilled in the art according to the actual circumstances. In some embodiments, the curing agent comprises one or more selected from the group consisting of: modified amine composite curing agents, polyamides, phenolic amines and aromatic amines; the second excipient comprises one or more selected from the group consisting of: ethanol, butanol and xylene or butyl acetate.
In the present application, the selection of the auxiliary agent is not particularly limited as long as the performance of the composition is not significantly affected, and for example, the antifoaming agent may be mineral oil, amide, lower alcohol, silicone antifoaming agent; the flatting agent can be selected from an organic silicon type and an acrylate type; the dispersant can be selected from fatty acid, aliphatic amide and ester dispersants; the toughening agent can be selected from carboxyl nitrile rubber, liquid nitrile rubber, polyvinyl butyral and the like; the coupling agent can be selected from silane coupling agent, titanate coupling agent and the like; the anti-settling agent can be selected from castor oil derivatives, fumed silica, organic argil, polyamide wax and the like; the antioxidant can be peroxide decomposition type antioxidant, phenol type antioxidant, etc.; the mildew preventive can be selected from barium metaborate, cuprous oxide, phenolic compounds, amine compounds and the like. The components and the proportion of the auxiliary agent can be reasonably selected by a person skilled in the art according to needs.
In some embodiments, the etherified modified phenolic resin and optionally the first adjuvant comprise 20 to 60 wt% of the first component, the pigment and filler comprise 20 to 46wt% of the first component, the adjuvant comprises 1 to 5wt% of the first component, the solvent comprises 0 to 50 wt% of the first component, and the curing agent comprises 5 to 25wt% of the first component.
In a fourth aspect of the present invention, there is provided a method for preparing an anticorrosive coating composition, comprising: preparing the etherified modified phenolic resin;
the etherified modified phenolic resin and one or more of the following components: mixing a pigment, a filler, an auxiliary agent, a solvent and a first auxiliary material to obtain a first component;
mixing the curing agent and optional second auxiliary materials to obtain a second component;
when in use, the first component and the second component are mixed to obtain the anticorrosive paint.
The ranges described above may be used alone or in combination. The present application can be more easily understood by the following examples.
Examples
The raw materials adopted in the embodiment of the application can all adopt common commercial sources, and part of the raw materials and the sources are as follows: BYK-410, BYK-358N, BYK-163, BYK-141 and BYK-A501 are all from BYK (Bike) of Germany, wherein BYK-410 is an anti-settling agent, BYK-358N is a leveling agent, BYK-163 is a dispersing agent, and BYK-141 and BYK-A501 are defoaming agents. The other raw materials are all commercial domestic raw materials, wherein the conductive powder is from Shanghai Junjiang chemical industry Co., Ltd, the polyamide, the phenolic amine and the aromatic amine are from Tianjin Yanan chemical plant, the titanium white is from Nanjing titanium dioxide factory in China, and the organic argil can be purchased from Heidis New Material Co., Ltd through the trade name of organic argil H-870.
Example 1 (phenol to phenol ether resin)
This example provides a phenol ether resin prepared by subjecting a phenol resin to an incomplete etherification condensation reaction by the following method:
phenol and formaldehyde are used as raw materials, and are subjected to polycondensation reaction for 3 hours at the normal pressure of 70-80 ℃ under the catalysis of an acidic ion exchanger to prepare the phenolic resin, wherein the reaction formula is as follows:
Figure 924234DEST_PATH_IMAGE016
after the catalyst is removed, under the conditions of normal pressure and 35-40 ℃, adding epoxy chloropropane according to 40% of the mole number of phenol, carrying out catalytic cyclization reaction in an alkaline ion exchange catalyst, removing the catalyst, and distilling to obtain the phenol ether resin. The reaction formula is as follows:
Figure 274444DEST_PATH_IMAGE017
the phenolic ether resin prepared by the method contains phenolic hydroxyl groups and epoxy ether groups, and the mole number of the phenolic hydroxyl groups is 150% of that of the epoxy ether groups.
Example 2 preparation of phenol Ether resin with cresol
This example provides a phenol ether resin prepared by subjecting a phenol resin to an incomplete etherification condensation reaction by the following method:
cresol and formaldehyde are used as raw materials, and are subjected to polycondensation reaction for 3 hours at 70-80 ℃ under normal pressure under the catalysis of an acidic ion exchanger to prepare the methyl phenolic resin, wherein the reaction formula is as follows:
Figure 223814DEST_PATH_IMAGE018
after the catalyst is removed, under the conditions of normal pressure and 35-40 ℃, epoxy chloropropane accounting for 60 percent of the mole number of cresol is added, catalytic cyclization reaction is carried out in an alkaline ion exchange catalyst, and the phenol ether resin is prepared by catalyst removal and distillation. The reaction formula is as follows:
Figure 139818DEST_PATH_IMAGE019
the phenolic ether resin prepared by the method contains phenolic hydroxyl groups and epoxy ether groups, and the mole number of the phenolic hydroxyl groups is 66% of that of the epoxy ether groups.
Example 3 preparation of etherification modified phenol resin from bisphenol A
This example provides a phenol ether resin prepared by subjecting a phenol resin to an incomplete etherification condensation reaction by the following method:
bisphenol A and formaldehyde are used as raw materials, and are subjected to polycondensation reaction for 3 hours at the normal pressure of 70-80 ℃ under the catalysis of an acidic ion exchanger to prepare bisphenol A phenolic resin, wherein the reaction formula is as follows:
Figure 14976DEST_PATH_IMAGE020
after the catalyst is removed, under the conditions of normal pressure and 35-40 ℃, adding epoxy chloropropane according to 120% of the mole number of bisphenol A, carrying out catalytic cyclization reaction in an alkaline ion exchange catalyst, removing the catalyst, and distilling to obtain the phenol ether resin. The reaction formula is as follows:
Figure 852482DEST_PATH_IMAGE021
the phenolic ether resin prepared by the method contains phenolic hydroxyl groups and epoxy ether groups, and the mole number of the phenolic hydroxyl groups is 66% of that of the epoxy ether groups.
Example 4 (anticorrosive coating composition)
The present example provides an anticorrosive coating composition comprising a first component and a second component, and a method of preparing the same.
The first component includes: 35wt% of phenolic ether resin, 15wt% of pigment, 27 wt% of filler, 3wt% of auxiliary agent and 20 wt% of solvent. The phenol ether resin was prepared as in example 1, the pigment was iron oxide red, and the filler consisted of: 14 wt% of mica powder, 5wt% of barium sulfate and 8 wt% of graphite, wherein the auxiliary agent comprises the following components: 2% of organic argil (anti-settling agent), 0.3% of BYK-4100.3%, 0.3% of BYK-358N and 1630.4%, wherein the solvent comprises the following components: 12.6% of dimethylbenzene, 5.4% of butanol and 2% of dibutyl phthalate.
The second component includes: curing agent and second auxiliary material. The curing agent is a modified amine composite curing agent which is 10wt% of the first component, and the second auxiliary material is butanol and xylene.
The anticorrosive coating composition is prepared by the following method:
the phenol ether resin was prepared as in example 1;
putting the prepared phenol ether resin into the solvent for dissolving;
adding iron oxide red, mica powder, barium sulfate and graphite into the dissolved phenol ether resin solution, uniformly stirring, grinding to 50-80 mu m by a sand mill, adding the auxiliary agent and the rest solution before discharging, uniformly stirring, filtering and barreling to obtain the first component.
And mixing the curing agent and a second auxiliary material to obtain a second component.
When in use, the first component and the second component are uniformly mixed and then can be coated.
Example 5 (anticorrosive coating composition)
The present example provides an anticorrosive coating composition comprising a first component and a second component, and a method of preparing the same.
The first component includes: 33wt% of phenolic ether resin, 20 wt% of pigment, 15wt% of filler, 2 wt% of auxiliary agent and 30 wt% of solvent. The phenol ether resin was prepared as in example 1, the pigment was titanium white, and the filler consisted of: 7 wt% of mica powder, 3wt% of calcined kaolin and 5wt% of barium sulfate, wherein the auxiliary agent comprises the following components: 0.8% of fumed silica (anti-settling agent), 0.4% of BYK-358N, 0.78% of BYK-1630.4% and 0.4% of BYK-1410.4%, wherein the solvent comprises the following components: 21% of dimethylbenzene and 9% of n-butyl alcohol.
The second component includes: curing agent and second auxiliary material. The curing agent is a modified amine composite curing agent which is 10wt% of the first component, and the second auxiliary material is butanol and xylene.
The anticorrosive coating composition is prepared by the following method:
the phenol ether resin was prepared as in example 1;
putting the prepared phenol ether resin into the solvent for dissolving;
adding titanium dioxide, mica powder, calcined kaolin and barium sulfate into the dissolved phenol ether resin solution, uniformly stirring, grinding to 50-80 mu m by a sand mill, adding the auxiliary agent and the rest solution before discharging, uniformly stirring, filtering and barreling to obtain the first component.
And mixing the curing agent and a second auxiliary material to obtain a second component.
When in use, the first component and the second component are uniformly mixed and then can be coated.
Example 6 (anticorrosive coating composition)
The embodiment provides the anticorrosive coating composition and a preparation method thereof, wherein the composition comprises a first component and a second component.
The first component includes: 33wt% of phenolic ether resin, 13 wt% of pigment, 24wt% of filler, 2 wt% of auxiliary agent and 28 wt% of solvent. The phenol ether resin was prepared as in example 2, the pigment was titanium white, and the filler consisted of: 18 wt% of conductive mica powder, 3wt% of calcined kaolin and 3wt% of barium sulfate, wherein the auxiliary agent comprises the following components: 0.8% of fumed silica (anti-settling agent), 0.4% of BYK-358N, 0.78% of BYK-1630.4% and 5010.4% of BYK-A, wherein the solvent comprises the following components: 20% of dimethylbenzene and 8% of n-butyl alcohol.
The second component includes: curing agent and second auxiliary material. The curing agent is a modified amine composite curing agent which is 10wt% of the first component, and the second auxiliary material is butanol and xylene.
The anticorrosive coating composition is prepared by the following method:
the phenol ether resin was prepared as in example 2;
putting the prepared phenol ether resin into the solvent for dissolving;
adding titanium dioxide, calcined kaolin and barium sulfate into the dissolved phenolic ether resin solution, uniformly stirring, grinding to 50-80 mu m by a sand mill, adding conductive mica powder, the auxiliary agent and the rest solution before discharging, uniformly stirring, filtering and barreling to obtain the first component.
And mixing the curing agent and a second auxiliary material to obtain a second component.
When in use, the first component and the second component are uniformly mixed and then can be coated.
Example 7 (anticorrosive coating composition)
The embodiment provides the anticorrosive coating composition and a preparation method thereof, wherein the composition comprises a first component and a second component.
The first component includes: 46wt% of phenolic ether resin, 6wt% of first auxiliary material, 19wt% of pigment, 25wt% of filler, 2 wt% of auxiliary agent and 2 wt% of solvent. The phenol ether resin was prepared as in example 3, the first adjuvant was an epoxy resin activator 696A (average molecular weight about 200), the pigment was iron oxide red, and the filler consisted of: 9wt% of mica powder, 8 wt% of graphite and 8 wt% of barium sulfate, wherein the auxiliary agent comprises the following components: 0.8% of organic argil (anti-settling agent), 0.4% of BYK-358N, 0.4% of BYK-1630.4% and 0.32% of BYK-1410.4%, wherein the solvent is dibutyl phthalate.
The second component includes: curing agent and second auxiliary material. The curing agent is a modified amine composite curing agent which is 15wt% of the first component, and the second auxiliary material is butanol and xylene.
The anticorrosive coating composition is prepared by the following method:
the phenol ether resin was prepared as in example 3;
putting the prepared phenol ether resin into an epoxy resin active agent 696A for dissolving;
adding iron oxide red, mica powder, graphite and barium sulfate into the dissolved phenol ether resin solution, uniformly stirring, grinding to 50-80 mu m by a sand mill, adding an auxiliary agent and dibutyl phthalate before discharging, uniformly stirring, filtering and barreling to obtain the first component.
And mixing the curing agent and a second auxiliary material to obtain a second component.
When in use, the first component and the second component are uniformly mixed and then can be coated.
The anticorrosive coating prepared in the embodiment is added with 6wt% of epoxy resin activator 696A, so that only 2 wt% of solvent is needed, the VOC content is low, the anticorrosive coating is an environment-friendly coating, and the temperature resistance is correspondingly low (120 ℃).
Performance detection
The technical indexes of the anticorrosive coating compositions described in examples 4, 5, 6 and 7 were measured according to the items and methods shown in the table:
TABLE 1
Figure 808806DEST_PATH_IMAGE022
TABLE 2
Figure 48157DEST_PATH_IMAGE023
Figure 362726DEST_PATH_IMAGE024
The data in the table show that the anticorrosive coating composition has excellent base material adhesion and good flexibility, the temperature resistance of a solvent-containing product reaches 150 ℃, the temperature resistance of an environment-friendly solvent-free product is 120 ℃, and the anticorrosive coating composition is high in acid and alkali resistance and suitable for corrosion prevention of storage tanks, pipelines and equipment for various oil products, chemicals, mixed sewage and other media.
The above description is intended to be exemplary of the present disclosure, and not to limit the scope of the present disclosure, which is defined by the claims appended hereto.

Claims (11)

1. An anticorrosive coating composition comprising a first component and optionally a second component,
the first component comprises: a phenolic ether resin, and one or more of the following components: a pigment, a filler, an auxiliary agent, a solvent, and a first auxiliary material;
the second component comprises a curing agent and optionally a second adjuvant,
the phenolic ether resin is obtained by carrying out incomplete etherification condensation reaction on phenolic resin, and is characterized in that the phenolic ether resin contains phenolic hydroxyl groups and epoxy ether groups, and the molar number of the phenolic hydroxyl groups is 5-600mol% of the epoxy ether groups.
2. The corrosion protective coating composition of claim 1 wherein the phenolic hydroxyl groups are present in a molar amount of 5 to 120 mole percent based on the epoxy ether groups.
3. The anticorrosive coating composition according to claim 1, wherein the molar number of phenolic hydroxyl groups is 100-600mol% of the epoxy ether groups.
4. The composition of claim 1, wherein,
the pigment comprises one or more selected from the group consisting of: titanium dioxide, zinc powder, iron oxide red, micaceous iron oxide, aluminum powder, zinc oxide, zinc phosphate, graphite and aluminum polyphosphate;
the filler comprises one or more selected from the group consisting of: static conductive powder, mica powder, titanium dioxide, barium sulfate, mica iron oxide, calcined kaolin, light calcium carbonate, quartz powder, diatomite, pulverized coal floating beads and pulverized coal sinking beads;
the adjuvant comprises one or more selected from the group consisting of: defoaming agent, flatting agent, dispersing agent, toughening agent, coupling agent, anti-settling agent, antioxidant and mildew preventive;
the solvent comprises one or more selected from the group consisting of: xylene, n-butanol, lipid solvents and ketone solvents;
the first excipient comprises one or more selected from the group consisting of: epoxy resin, novolac epoxy resin, silicone resin;
the curing agent comprises one or more selected from the group consisting of: modified amine composite curing agent, polyamide, phenolic amine, aromatic amine, aliphatic amine and alicyclic amine;
the second excipient comprises one or more selected from the group consisting of: ethanol, butanol and xylene or butyl acetate.
5. The composition according to claim 4, wherein,
the phenolic ether resin and the optional first auxiliary material account for 20-60 wt% of the first component,
the pigment and filler comprise 20 to 46wt% of the first component,
the auxiliary agent accounts for 1-5 wt% of the first component,
the solvent is 0-50 wt% of the first component,
the curing agent is 5-50 wt% of the first component.
6. The corrosion protective coating composition of claim 1 wherein said phenolic ether resin has the formula:
Figure DEST_PATH_IMAGE002
，
Figure DEST_PATH_IMAGE004
，
Figure DEST_PATH_IMAGE006
，
or a mixture comprising at least one of the foregoing.
7. The corrosion protective coating composition of claim 1 wherein the structure of the phenolic resin comprises at least one selected from the group consisting of:
Figure DEST_PATH_IMAGE008
，
Figure DEST_PATH_IMAGE010
，
Figure DEST_PATH_IMAGE012
。
8. a method of making the composition of any one of claims 1 to 7, comprising:
preparing the phenol ether resin;
mixing the phenolic ether resin and one or more selected from pigments, fillers, auxiliaries, solvents and first auxiliary materials to obtain a first component;
and mixing the curing agent and optional second auxiliary materials to obtain a second component.
9. The method of claim 8, comprising:
and carrying out condensation reaction on the phenolic resin and epoxy chloropropane to obtain the phenolic ether resin.
10. The process of claim 9, wherein the moles of epichlorohydrin are less than the moles of phenolic hydroxyl groups in the phenolic resin.
11. The process of claim 10, wherein the phenolic hydroxyl groups in the phenolic resin are 105 to 700 mol% of epichlorohydrin.
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